The present invention relates to a method for processing silver halide photographic light sensitive materials and in particular to a method for processing a silver halide photographic light sensitive material exhibiting higher sensitivity in the red to near infrared region for use in an image setter or facsimile plotter, resulting in little residual color stain when processed in a developer containing an ascorbic acid type developing agent, and exhibiting superior process stability.
Photographic materials having photographic characteristics such as ultra-high contrast are broadly employed as a photographic material used in the field of printing plate making. To obtain such high contrast images, there are known an image forming method of processing photographic materials containing hydrazine derivatives with a so-called MQ developer solution (i.e., developer solution by the combined use of hydroquinone and p-amiophenols) or a PQ developer solution (i.e., developer solution by the combined use of hydroquinone and 1-phenyl-3-pyrazolodones) to form an ultra-high contrast image, as described in U.S. Pat. No. 4,269,929 and JP-A Nos. 60-258537 and 5-232616 (hereinafter, the term, JP-A refers to a unexamined, published Japanese Patent Application). In such an image forming method, however, hydroquinone is used as a developing agent, and it is a concern that hydroquinone is not suitable from the ecological or toxicological point of view. It is therefore an aim to achieve a method of forming ultra-high contrast images with a developer solution containing no hydroquinone.
U.S. Pat. Nos. 5,236,816 and 5,264,323 describe a system in which ascorbic acids are employed as a developing agent. However, problems arise with the use of ascorbic acids as a developing agent in that the pH of a developer is easily lowered through processing and aerial oxidation and process variation is quite marked. There is a problem that the use of ascorbic acid developing agents increases residual color-staining caused by sensitizing dyes, and consequently an improvement thereof is desired. Further, the use of ascorbic acid developing agents produces silver precipitates in the fixer bath, which adheres to photographic materials as silver sludge, and reduction of such sludge is also desired.
In view of the foregoing problems, it is an object of the present invention to provide a method for processing a silver halide photographic light sensitive material for use in graphic arts, achieving a decrease in residual dye staining after processing, leading to enhanced sensitivity and contrast, and also superior halftone dot quality and practical density within the red to infrared wavelength region, and producing little sludge.
The object of the present invention can be accomplished by the following constitution:
1. a method of processing a silver halide photographic light sensitive material comprising the steps of:
developing the silver halide photographic material with a developer solution,
fixing the developed silver halide photographic material with a fixer solution, and
washing the fixed silver halide photographic material with a washing water,
wherein the silver halide photographic material comprises a support and a light sensitive silver halide emulsion layer containing a spectral-sensitizing dye represented by the following formula (1-a), (1-b), (2), (3-a), (3-b), (4) or (5),
and wherein the developer solution contains a developing agent represented by formula (A), and at least one of the developer and fixer solutions is replenished at a replenishing rate which has been determined in accordance with the proportion of an exposed area per unit area of the photographic material: 
wherein Y21, Y22, Y23 and Y24 each represent xe2x80x94N(R24)xe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94Sexe2x80x94 or xe2x80x94Texe2x80x94, provided that one of Y23 and Y24 is xe2x80x94N(R24)xe2x80x94, and all of Y21, Y22 and Y23 or all of Y21, Y22 and Y24 are not xe2x80x94Sxe2x80x94; R21 represents an aliphatic group having 8 or less carbon atoms and containing an aqueous solubility promoting group; R22, R23 and R24 each represent a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, provided that at least two of R22, R23 and R24 are substituted with an aqueous solubility promoting group; Z21 represent a non-metallic atom group necessary to form a 5- or 6-membered nitrogen-containing heterocyclic ring, which may be condensed; W21 represents an oxygen atom, sulfur atom, =N(Ar) or =C less than (E21) (E22), in which Ar represents an aromatic ring group or a heterocyclic group, E21 and E22 represent an electron-withdrawing group or combine with each other to form a heterocyclic ring containing an oxo group or an acidic heterocyclic ring; L21 and L22 represent a substituted or unsubstituted methine group; 121 is 0 or 1; M21 represent an ion necessary to counterbalance a total intramolecular charge; and n21 represents a number of ion necessary to counterbalance a total intramolecular charge; 
wherein Y25, Y26 and Y27 each represent xe2x80x94N(R29)xe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, or xe2x80x94Sexe2x80x94; R25 represents an aliphatic group having 8 or less carbon atoms and containing an aqueous solubility promoting group; R26, R27, R28 and R29 represent a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, provided that at least three of R26, R27, R28 and R29 are substituted with an aqueous solubility promoting group; Z22 represent a non-metallic atom group necessary to form a 5- or 6-membered nitrogen-containing heterocyclic ring, which may be condensed; L23 and L24 represent a substituted or unsubstituted methine group; M22 represent an ion necessary to counterbalance a total intramolecular charge; and n22 represents a number of ion necessary to counterbalance a total intramolecular charge; 
wherein Y31, Y32 and Y33 each represent xe2x80x94N(R34)xe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, or xe2x80x94Sexe2x80x94; R31 represents an aliphatic group having 10 or less carbon atoms and substituted with an aqueous solubility promoting group; R32, R33 and R34 represent a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, provided that at least two of R32, R33 and R34 are substituted an aqueous solubility promoting group; V31 and V32 each represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryl group, or V31 and V32 combine with each other to form a ring condensed with an azole ring; L31 and L32 represent a substituted or unsubstituted methine group; M31 represent an ion necessary to compensate a total intramolecular charge; and n31 represents a number of ion necessary to counterbalance a total intramolecular charge; 
wherein Y41 and Y42 each represent xe2x80x94N(R44)xe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94Sexe2x80x94 or xe2x80x94Texe2x80x94; R41 represents an aliphatic group having 8 or less carbon atoms and substituted with an aqueous solubility promoting group; R42, R43 and R44 represent a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, provided that at least two of R42, R43 and R44 are substituted with an aqueous solubility promoting group; Z41 represent a non-metallic atom group necessary to form a 5- or 6-membered nitrogen-containing heterocyclic ring, which may be condensed; W41 represents an oxygen atom, sulfur atom, =N(Ar) or =C less than (E21)(E22), in which Ar represents an aromatic ring group or a heterocyclic group, E41 and E42 represent an electron-withdrawing group or E41 and E42 combine with each other to form a heterocyclic; L41, L42, L43 and L44 represent a substituted or unsubstituted methine group; 141 is 0 or 1; M41 represent an ion necessary to counterbalance a total intramolecular charge; and n41 represents a number of ion necessary to counterbalance a total intramolecular charge; 
wherein Z42 represent a non-metallic atom group necessary to form a 5- or 6-membered nitrogen-containing heterocyclic ring, which may be condensed; Y43 and Y44 each represent xe2x80x94N (R48)xe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94Sexe2x80x94 or xe2x80x94Texe2x80x94; R45 represents an aliphatic group having 8 or less carbon atoms and substituted with an aqueous solubility promoting group; R46, R47 and R48 represent a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, provided that at least two of R46, R47 and R48 are substituted with an aqueous solubility promoting group; Z42 represent a non-metallic atom group necessary to form a 5- or 6-membered nitrogen-containing heterocyclic ring, which may be condensed; W42 represents an oxygen atom or sulfur atom; L45, L46, L47 and L48 represent a substituted or unsubstituted methine group, provided that at least one of L45, L46, L47 and L48 is a substituted methine group; M42 represent an ion necessary to counterbalance a total intramolecular charge; and n42 represents a number of ion necessary to counterbalance a total intramolecular charge; 
wherein R51 represents an aliphatic group having 10 or less carbon atoms and substituted with an aqueous solubility promoting group; R52, R53 and R54 represent a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, provided that at least two of R52, R53 and R54 are substituted with an aqueous solubility promoting group; V51 and V52 represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryl group, or V51 and V52 combine with each other to form a ring condensed with an azole ring; W51 represents an oxygen atom, sulfur atom, =N(Ar) or =C less than (E21)(E22), in which Ar represents an aromatic ring group or a heterocyclic group, E21 and E22 represent an electron-withdrawing group or E21 and E22 combine with each other to form a heterocyclic ring containing an oxo group or an acidic heterocyclic ring; L51 and L52 represent a substituted or unsubstituted methine group; M51 represent an ion necessary to counterbalance a total intramolecular charge; and n51 represents a number of ion necessary to counterbalance a total intramolecular charge; 
wherein R61 and R62 represent a substituted or unsubstituted alkyl group, provided that at least one of R61 and R62 is substituted with an aqueous solubility promoting group; V61, V62, V63 and V64 represent a hydrogen atom or a univalent substituent group, provided that any two of V61, V62, V63 and V64 do not combine with each other to form a ring and the sum of molecular weights of V61, V62, V63 and V64 is 4 to 50; L61, L62, L63 and L64 represent a methine group; M61 represents an ion necessary to counterbalance a total intramolecular charge; and n61 represents a number of ion necessary to counterbalance a total intramolecular charge; and 
wherein R1 and R2 represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group or a substituted or unsubstituted alkylthio group, or R1 and R2 combine with each other to form a ring; k is 0 or 1; when k is 1, X represents xe2x80x94COxe2x80x94 or xe2x80x94CSxe2x80x94; M1 and M2 represent a hydrogen atom or an alkali metal atom;
2. The processing method of a silver halide photographic material described above, wherein a swelling percentage of the light sensitive silver halide emulsion layer side is 10 to 100%;
3. The processing method of a silver halide photographic material described in 1, wherein the silver halide emulsion layer contains a hydrazine derivative;
4. The processing method of a silver halide photographic material described in 1, wherein the silver halide photographic material comprises a hydrophilic colloidal layer which is adjacent to the silver halide emulsion layer, the hydrophilic colloidal layer containing a hydrazine derivative;
5. The processing method of a silver halide photographic material described in 1, wherein the developer solution is replenished at a replenishing rate which is determined based on an exposed area rate per unit area of the photographic material, the replenishing rate of the developer solution being 30 to 250 ml per m2 of the photographic material;
6. The processing method of a silver halide photographic material described in 1, wherein the developer solution is replenished at a replenishing rate which is determined based on an exposed area rate per unit area of the photographic material, a developer replenishing solution exhibiting a pH higher by 0 to 0.5 than that of the developer solution at the start of development;
7. The processing method of a silver halide photographic material described in 1, wherein the fixer solution is replenished at a replenishing rate which is determined based on an exposed area rate per unit area of the photographic material, the replenishing rate of the fixer solution being 30 to 300 ml per m2 of the photographic material;
8. a method of processing a silver halide photographic light sensitive material comprising on one side of a support a light sensitive silver halide emulsion layer and on the other side a backing layer, wherein the light-sensitive layer contains a spectral-sensitizing dye represented by the following formula (1-a) or (1-b); a developer solution contains a developing agent represented by formula (A); and the replenishing rate of a processing solution is determined based on the proportion of an exposed area per unit area of the photographic material to perform replenishment: 
wherein Y21, Y22, Y23 and Y24 each represent xe2x80x94N(R24)xe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94Sexe2x80x94 or xe2x80x94Texe2x80x94, provided that one of Y23 and Y24 is xe2x80x94N(R24)xe2x80x94, and Y21, Y22 and Y23, or Y21, Y22 and Y24 are not xe2x80x94Sxe2x80x94 at the same time; R21 represents an aliphatic group having 8 or less carbon atoms and containing an aqueous solubility promoting group; R22, R23 and R24 represent an aliphatic group, an aryl group or a heterocyclic group, provided that at least two of R22, R23 and R24 contain an aqueous solubility promoting group; Z21 represent a non-metallic atom group necessary to form a 5- or 6-membered nitrogen-containing heterocyclic ring, which may be condensed; W21 represents an oxygen atom, sulfur atom, =N(Ar) or =C less than (E21)(E22), in which Ar represents an aromatic ring group or a heterocyclic group, E21 and E22 represent an electron-withdrawing group or combine with each other to form a heterocyclic ring containing an oxo group or an acidic heterocyclic ring ; L21 and L22 represent a substituted or unsubstituted methine group; 121 is 0 or 1; M21 represent an ion necessary to counterbalance a total intramolecular charge; and n21 represents a number of ion necessary to counterbalance a total intramolecular charge; 
wherein Y25, Y26 and Y27 each represent xe2x80x94N(R29)xe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, or xe2x80x94Sexe2x80x94; R25 represents an aliphatic group having 8 or less carbon atoms and containing an aqueous solubility promoting group; R26, R27, R28 and R29 represent an aliphatic group, an aryl group or a heterocyclic group, provided that at least three of R26, R27, R28 and R29 contain an aqueous solubility promoting group; Z22 represent a non-metallic atom group necessary to form a 5- or 6-membered nitrogen-containing heterocyclic ring, which may be condensed; L23 and L24 represent a substituted or unsubstituted methine group; M22 represent an ion necessary to counterbalance a total intramolecular charge; and n22 represents a number of ion necessary to counterbalance a total intramolecular charge; 
wherein R1 and R2 represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group or a substituted or unsubstituted alkylthio group, or R1 and R2 may combine with each other to form a ring; k is 0 or 1; when k is 1, X represent xe2x80x94COxe2x80x94 or xe2x80x94CSxe2x80x94; M1 and M2 represent a hydrogen atom or an alkali metal atom;
9. a method of processing a silver halide photographic light sensitive material comprising on one side of a support a light sensitive silver halide emulsion layer and on the other side a backing layer, the light-sensitive layer contains a spectral-sensitizing dye represented by the following formula (2); a developer solution contains a developing agent represented by formula (A) described above; and the replenishing rate of a processing solution is determined based on the proportion of an exposed area per unit area of the photographic material to perform replenishment: 
wherein Y31, Y32 and Y33 each represent xe2x80x94N(R34)xe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, or xe2x80x94Sexe2x80x94; R31 represents an aliphatic group having 10 or less carbon atoms and containing an aqueous solubility promoting group; R32, R33 and R34 represent an aliphatic group, an aryl group or a heterocyclic group, provided that at least two of R32, R33 and R34 contain an aqueous solubility promoting group; V31 and V32 each represent a hydrogen atom, an alkyl group, an alkoxy group, or an aryl group, or V31 and V32 combine with each other to form a ring condensed with an azole ring; L31 and L32 represent a substituted or unsubstituted methine group; M31 represent an ion necessary to compensate a total intramolecular charge; and n31 represents a number of ion necessary to counterbalance a total intramolecular charge;
10. a method of processing a silver halide photographic light sensitive material comprising on one side of a support a light sensitive silver halide emulsion layer and on the other side a backing layer, the light-sensitive layer contains a spectral-sensitizing dye represented by the following formula (3-a) or (3-b); a developer solution contains a developing agent represented by formula (A) described above; and the replenishing rate of a processing solution is determined based on the proportion of an exposed area per unit area of the photographic material to perform replenishment: 
wherein Z41 represent a non-metallic atom group necessary to form a 5- or 6-membered nitrogen-containing heterocyclic ring, which may be condensed; Y41 and Y42 each represent xe2x80x94N(R44)xe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94Sexe2x80x94 or xe2x80x94Texe2x80x94; R41 represents an aliphatic group having 8 or less carbon atoms and containing an aqueous solubility promoting group; R42, R43 and R44 represent an aliphatic group, an aryl group or a heterocyclic group, provided that at least two of R42, R43 and R44 contain an aqueous solubility promoting group; W41 represents an oxygen atom, sulfur atom, =N(Ar) or =C less than (E21) (E22), in which Ar represents an aromatic ring group or a heterocyclic group, E41 and E42 represent an electron-withdrawing group or E41 and E42 each represent non-metallic atom group and combine with each other to form a heterocyclic; L41, L42, L43 and L44 represent a substituted or unsubstituted methine group; 141 is 0 or 1; M41 represent an ion necessary to counterbalance a total intramolecular charge; and n41 represents a number of ion necessary to counterbalance a total intramolecular charge; 
wherein Z42 represent a non-metallic atom group necessary to form a 5- or 6-membered nitrogen-containing heterocyclic ring; Y43 and Y44 each represent xe2x80x94N(R48)xe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94Sexe2x80x94 or xe2x80x94Texe2x80x94; R45 represents an aliphatic group having 8 or less carbon atoms and containing an aqueous solubility promoting group; R46, R47 and R48 represent an aliphatic group, an aryl group or a heterocyclic group, provided that at least two of R46, R47 and R48 contain an aqueous solubility promoting group; W42 represents an oxygen atom or sulfur atom; L45, L46, L47 and L48 represent a substituted or unsubstituted methine group, provided that at least one of L45, L46, L47 and L48 is a substituted methine group; M42 represent an ion necessary to counterbalance a total intramolecular charge; and n42 represents a number of ion necessary to counterbalance a total intramolecular charge;
11. a method of processing a silver halide photographic light sensitive material comprising on one side of a support a light sensitive silver halide emulsion layer and on the other side a backing layer, the light-sensitive layer contains a spectral-sensitizing dye represented by the following formula (4); a developer solution contains a developing agent represented by formula (A) described above; and the replenishing rate of a processing solution is determined based on the proportion of an exposed area per unit area of the photographic material to perform replenishment: 
wherein R51 represents an aliphatic group having 10 or less carbon atoms and containing an aqueous solubility promoting group; R52, R53 and R54 represent an aliphatic group, an aryl group or a heterocyclic group, provided that at least two of R52, R53 and R54 contain an aqueous solubility promoting group; V51 and V52 represent a hydrogen atom, an alkyl group, an alkoxy group, or an aryl group, or V51 and V52 combine with each other to form a ring condensed with an azole ring; W51 represents an oxygen atom, sulfur atom, =N(Ar) or =C less than (E21)(E22), in which Ar represents an aromatic ring group or a heterocyclic group, E21 and E22 represent an electron-withdrawing group or combine with each other to form a heterocyclic ring containing an oxo group or an acidic heterocyclic ring; L51 and L52 represent a substituted or unsubstituted methine group; M51 represent an ion necessary to counterbalance a total intramolecular charge; and n51 represents a number of ion necessary to counterbalance a total intramolecular charge;
12. a method of processing a silver halide photographic light sensitive material comprising on one side of a support a light sensitive silver halide emulsion layer and on the other side a backing layer, the light-sensitive layer contains a spectral-sensitizing dye represented by the following formula (5); a developer solution contains a developing agent represented by formula (A) described above; and the replenishing rate of a processing solution is determined based on the proportion of an exposed area per unit area of the photographic material to perform replenishment: 
wherein R61 and R62 represent an alkyl group containing an aqueous solubility promoting group, which may be in a free form or a salt form; V61, V62, V63 and V64 represent a hydrogen atom or a univalent substituent group, provided that these substituent groups do not form a ring and the sum of molecular weights of V61, V62, V63 and V64 is 4 to 50; L61, L62, L63 and L64 represent a methine group; M61 represents an ion necessary to counterbalance a total intramolecular charge; and n61 represents a number of ion necessary to counterbalance a total intramolecular charge;
13. The processing method of a silver halide photographic material described in any one of 8 through 12, wherein the swelling percentage of the light sensitive silver halide emulsion layer side is 10 to 100%;
14. The processing method of a silver halide photographic material described in any one of 8 through 13, wherein the silver halide emulsion layer or a hydrophilic colloid layer adjacent thereto contains a hydrazine derivative;
15. The processing method of a silver halide photographic material described in any one of 8 through 14, wherein the processing solution which is replenished at a rate proportional to the exposed area is a developer solution and the developer replenishing rate is 30 to 250 ml per m2 of the photographic material;
16. The processing method of a silver halide photographic material described in any one of 8 through 15, wherein a developer replenishing solution exhibits a pH higher by 0 to 0.5 than that of a developer solution at the start of development;
17. The processing method of a silver halide photographic material described in any one of 8 through 16, wherein the processing solution which is replenished at a rate porportional to the exposed area is a fixer solution and the fixer replenishing rate is 30 to 300 ml per m2 of the photographic material.
The spectral sensitizing dyes represented by formula (1-a) or (1-b) will be described.
In formula (1-a) or (1-b), Y21, Y22, Y23, Y24, Y25, Y26 and Y27 each represent xe2x80x94NR24 or xe2x80x94NR29, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, or xe2x80x94Sexe2x80x94. The aqueous solubility promoting group contained in R21, R22, R23, R24, R25, R26, R27, R28 or R29 include, for example, a sulfo group, a carboxy group, a phosphono group, a sulfate group and a sulfino group. The aliphatic group represented by R21, R22, R23, R24, R25, R26, R27, R28 or R29 include, for example, a straight or branched alkyl group having 1 to 8 carbon atoms (such as methyl, ethyl, n-propyl, n-pentyl, isobutyl), an alkenyl group having 3 to 8 carbon atoms (such as 3-butenyl, 2-propenyl), and an aralkyl group having 7 to 10 carbon atoms (such as benzyl, phenethyl). The aryl group represented by R21, R22, R23, R24, R25, R26, R27, R28 or R29 include, for example, a phenyl group and the heterocyclic group include, for example, pyridyl group (e.g., 2- or 4-pyridyl), pyrazyl group, furyl group (e.g., 2-furyl), thienyl group (e.g., 2-thienyl), sulforanyl group, tetrahydrofuryl group, piperidyl group, pyrrolyl group, and imidazolyl group. R21, R22, R23, R24, R25, R26, R27, R28 or R29 each may be substituted and examples of the substituent group include a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), an alkoxy group (e.g., methoxy, ethoxy), an aryloxy group (e.g., phenoxy, p-tolyoxy), cyano group, a carbamoyl group (e.g., carbamoyl, N-methylcarbamoyl, N,N-tetramethylenecarbamoyl), a sulfamoyl group (e.g., sulfamoyl, N,N-3-oxapentamethyleneaminosulfonyl), a methanesulfonyl group, an alkoxycarbonyl group (e.g., ethoxycarbonyl, butoxycarbonyl), an aryl group (e.g., phenyl, carboxyphenyl), and an acyl group (e.g., acetyl, benzoyl). Exemplary examples of the aliphatic group containing an aqueous solubility promoting group include carboxymethyl, sulfoethyl, sulfopropyl, sulfobutyl, sulfopentyl, 3-sulfobutyl, 6-sulfo-3-oxahexyl, xcfx89-sulfopropoxycarbonylmethyl, xcfx89-sulfopropylaminocarbonyl-methyl, N-ethyl-N-sulfopropyl, 3-sulfinobutyl, 3-phosphonopropyl, 4-sulfo-3-butenyl, 2-carboxy-2propenyl, o-sulfobenzyl, p-sulfophenethyl, and p-carboxybenzyl. Examples of the aryl group containing an aqueous solubility promoting group include p-sulfophenyl and p-carboxyphenyl; and examples of the heterocyclic group containing an aqueous solubility promoting group include 4-sulfothienyl and 3-carboxypyridyl. Of these, it is preferred that R21 and R25 are a sulfo group containing alkyl group, and at least two of R22, R23, R24, R25, R26, R27, R28 or R29 are carboxymethyl.
Z21 and Z22 each represent a 5- or 6-membered nitrogen-containing heterocyclic group. The nitrogen-containing heterocyclic rings include basic nitrogen-containing heterocyclic rings forming a cyanine dye, such as an oxazole ring (e.g., oxazole, benzoxazole, naphthoxazole), a thiazole ring (e.g., thiazolidine, thiazole, benzthiazole, naphthothiazole), an imidazole ring (e.g., imidazole, benzimidazole, naphthoimidazole), a selenazole ring (e.g., selenazole, benzoselenazole, naphthoselenazole), a tetrazole ring (e.g., tetrazole, benztetrazole, naphthotetrazole), a pyrydine ring (e.g., pyridine quinoline), and pyrrole ring (e.g., pyrrole, indole, indolenine). The nitrogen-containing heterocyclic group represented by Z21 or Z22 may be substituted at any position on the heterocyclic ring.
Examples of the substituent group include a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom9, trifluoromethyl, an alkoxy group (e.g., unsubstituted alkoxy such as methoxy, ethoxy and butoxy, and substituted alkoxy such as 2-methoxyethoxy and benzoyloxy), hydroxy, cyano, an aryloxy group (e.g., phenoxy, tolyloxy), an aryl group (e.g., phenyl, p-chlorophenyl, p-tolyl, p-methoxyphenyl), styryl group, a heterocyclic group (e.g., furyl, thienyl9, a carbamoyl group (e.g., carbamoyl, N-ethylcarbamoyl), a sulfamoyl group (e.g., sulfamoyl, N,N-dimethylsulfamoyl), an acylamino group (e.g., acetylamino, propionylamino, benzoylamino), an acyl group (e.g., acetyl, benzoyl), an alkoxycarbonyl group (e.g., ethoxycarbonyl), a sulfonamido group (e.g., methanesulfonamido, p-toluenesulfonamido), carboxy group, and an alkyl group (e.g., methyl, ethyl, isopropyl).
L21, L22, L23 and L24 represent an unsubstituted or substituted methine group. The substituent group thereof include, for example, an alky group (e.g., methyl, ethyl), a pahenyl group (e.g., phenyl, carboxyphenyl), an alkoxy group (e.g., methoxy, ethoxy), an aryloxy group (e.g., phenoxy, carboxyphenoxy), an aralkyl group (e.g., benzyl) and a fluorine atom. The sensitizing dye of the invention, in which either L21 or L22 is a substituted methine group achieves higher spectral sensitivity and exhibits characteristics such that a dye is easily bleached in a processing solution, advantageously leading to reduced dye staining.
The electron-withdrawing group represented by E21 and E22 is selected from the groups exhibiting a Hammett "sgr"p value of 0.3 or more, and examples thereof include cyano group, a carbamoyl group (e.g., carbamoyl, morpholinocarbamoyl, N-methylcarbamoyl), an alkoxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl), a sulfamoyl group (e.g., sulfamoyl, morpholinosulfonyl, N,N-dimethylsulfamoyl), an acyl group (e.g., acetyl, benzoyl), and a sulfonyl group (e.g., methanesulfonyl, ethanesulfonyl, benzenesulfonyl, toluenesulfonyl). The Hammett "sgr"p value is a substituent constant which is determined from electromeric effect of a substituent affecting hydrolysis of a benzoic acid ester, as detailed in J. Org. Chem. 23, 420-427 (1958); xe2x80x9cZikken-Kagaku Kozaxe2x80x9d vol. 14 (published by Maruzen); Physical Organic Chemistry (McGraw Hill Book Co., 1940); Drag Design vol. VII (Academic Press, New York, 1976) and xe2x80x9cYakubutsu -no Kozokasseixe2x80x9d (Nankodo, 1979). Examples an oxo-group containing heterocyclic ring and an acidic heterocyclic group include the following: 
wherein Ra and Rb each represent a lower alkyl group, an aryl group or a heterocyclic group. The lower alkyl group include substituted and unsubstituted ones, for example, methyl, ethyl, propyl, 2-hydroxyethyl, 2-methoxyethyl, trifluoromethyl, carboxymethyl, carboxymethyl, 2-sulfoethyl and benzyl. The aryl group and heterocyclic group represented by Ra and Rb include the same as defined in R21, R22, R23, R24, R25, R26, R27, R28 or R29.
M21 and M22 represent a cation or an acid anion. Examples of the cation include proton, organic ammonium ion (e.g., triethylammonium, triethanolammonium), inorganic cations (e.g., lithium, sodium or calcium ion). Examples of the acid anion include a halide ion (e.g., chloride ion, bromide ion, iodide ion), p-toluenesulfonate ion, perchlorate ion, and 4-fluoroborate ion. n21 and n22 represent the number of ion(s) forming an intramolecular salt and counterbalancing the total intramolecular charge.
Examples of the spectral sensitizing dyes represented by formula (1-a) or (1-b) are shown below but are by no means limited to these compounds. 
The foregoing compounds can be readily synthesized according the commonly known methods, as described in F. M. Hamer xe2x80x9cCyanine Dyes and Related Compoundsxe2x80x9d (Interscience Publishers, 1964), U.S. Pat. Nos. 2,454,629 and 2,493,748; British Patent No. 489,335 and European Patent No. 730,008.
The sensitizing dyes represented by formula (2) will be described. In formula (2), Y31, Y32 and Y33 represent xe2x80x94N(R34)xe2x80x94, xe2x80x94Oxe2x80x94. xe2x80x94Sxe2x80x94 or xe2x80x94Sexe2x80x94. The aqueous solubility promoting group contained in R31, R32 and R33 include, for example, a sulfo group, carboxy group, phosphono group, sulfate group and sulfino group. The aliphatic group represented by R31, R32 and R33 include, for example, a straight or branched alkyl group having 1 to 10 carbon atoms (such as methyl, ethyl, n-propyl, n-pentyl, isobutyl), an alkenyl group having 3 to 10 carbon atoms (such as 3-butenyl, 2-propenyl), and an aralkyl group having 7 to 10 carbon atoms (such as benzyl, phenethyl). The aryl group represented by R31, R32 and R33 include, for example, a phenyl group and the heterocyclic group include, for example, pyridyl group (e.g., 2- or 4-pyridyl), pyrazyl group, furyl group (e.g., 2-furyl), thienyl group (e.g., 2-thienyl), sulforanyl group, tetrahydrofuryl group, piperidyl group, pyrrolyl group, and imidazolyl group.
R31, R32 and R3 each may be substituted and examples of the substituent group include a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), an alkoxy group (e.g., methoxy, ethoxy), an aryloxy group (e.g., phenoxy, p-tolyoxy), cyano group, a carbamoyl group (e.g., carbamoyl, N-methylcarbamoyl, N,N-tetramethylenecarbamoyl), a sulfamoyl group (e.g., sulfamoyl, N,N-3-oxapentamethyleneaminosulfonyl), a methanesulfonyl group, an alkoxycarbonyl group (e.g., ethoxycarbonyl, butoxycarbonyl), an aryl group (e.g., phenyl, carboxyphenyl), and an acyl group (e.g., acetyl, benzoyl). Exemplary examples of the aliphatic group containing an aqueous solubility promoting group include carboxymethyl, sulfoethyl, sulfopropyl, sulfobutyl, sulfopentyl, 3-sulfobutyl, 6-sulfo-3-oxahexyl, xcfx89-sulfopropoxycarbonylmethyl, xcfx89-sulfopropylaminocarbonyl-methyl, N-ethyl-N-sulfopropyl, 3-sulfinobutyl, 3-phosphonopropyl, 4-sulfo-3-butenyl, 2-carboxy-2propenyl, o-sulfobenzyl, p-sulfophenethyl, and p-carboxybenzyl. Examples of the aryl group containing an aqueous solubility promoting group include p-sulfophenyl and p-carboxyphenyl; and examples of the heterocyclic group containing an aqueous solubility promoting group include 4-sulfothienyl and 3-carboxypyridyl.
The alkyl group represented by V31 and V32 include straight or branched alkyl groups, such as methyl, ethyl, isopropyl, t-butyl, iso-butyl, t-pentyl and hexyl. The alkoxy group represented by V31 and V32 include, for example, methoxy, ethoxy, and propoxy. The aryl group represented by V31 and V32, which may be substituted at any position include, for example, phenyl, p-tolyl, p-hydroxyphenyl, and p-methoxyphenyl. The condensed azole ring formed by the combination of V31 and V32 include, for example, 4,5,6,7-tetrahydrobenzoxazole, naphtha[1,2-d]oxazole, naphtha[2,3-d]oxazole, benzothiazole, 4,5,6,7-tetrahydrobenzothiazole, naphtha[1,2-d]thiazole, naphtha[2,3-d]thiazole, benzoselenazole and naphtha[1,2-d]selenazole. The group represented by V31 and V32 or the condensed ring formed by V31 and V32 may be substituted by a substituent group at any position thereof.
Examples of the substituent group include a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom9, trifluoromethyl, an alkoxy group (e.g., unsubstituted alkoxy such as methoxy, ethoxy and butoxy, and substituted alkoxy such as 2-methoxyethoxy and benzoyloxy), hydroxy, cyano, an aryloxy group (e.g., phenoxy, tolyloxy), an aryl group (e.g., phenyl, p-chlorophenyl, p-tolyl, p-methoxyphenyl), styryl group, a heterocyclic group (e.g., furyl, thienyl9, a carbamoyl group (e.g., carbamoyl, N-ethylcarbamoyl), a sulfamoyl group (e.g., sulfamoyl, N,N-dimethylsulfamoyl), an acylamino group (e.g., acetylamino, propionylamino, benzoylamino), an acyl group (e.g., acetyl, benzoyl), an alkoxycarbonyl group (e.g., ethoxycarbonyl), a sulfonamido group (e.g., methanesulfonamido, p-toluenesulfonamido), carboxy group, and an alkyl group (e.g., methyl, ethyl, isopropyl).
L31 and L32 represent an unsubstituted or substituted methine group. The substituent group thereof include, for example, an alky group (e.g., methyl, ethyl), a pahenyl group (e.g., phenyl, carboxyphenyl), an alkoxy group (e.g., methoxy, ethoxy), an aryloxy group (e.g., phenoxy, carboxyphenoxy), and an aralkyl group (e.g., benzyl).
M31 represent a cation or an acid anion. Examples of the cation include proton, organic ammonium ion (e.g., triethylammonium, triethanolammonium), inorganic cations (e.g., lithium, sodium or calcium ion). Examples of the acid anion include a halide ion (e.g., chloride ion, bromide ion, iodide ion), p-toluenesulfonate ion, perchlorate ion, and 4-fluoroborate ion. n31represents the number of ion(s) forming an intramolecular salt and counterbalancing the total intramolecular charge.
In formula (2), R31 is preferably a sulfo-substituted alkyl group and at least two of R32, R33 and R34 is preferably substituted by a carboxymethyl group.
Examples of the spectral sensitizing dyes represented by formula (2) are shown below but are by no means limited to these compounds. 
The foregoing compounds can be readily synthesized according the commonly known methods, as described in F. M. Hamer xe2x80x9cCyanine Dyes and Related Compoundsxe2x80x9d (Interscience Publishers, 1964), and U.S. Pat. Nos. 2,454,629 and 2,493,748.
The spectral sensitizing dyes represented by formula (3-a) or (3-b) will be described.
In formula (3-a) or (3-b), the aliphatic group represented by R41, R42, R43, R44, R45, R46, R47 or R48 include, for example, a straight or branched alkyl group having 1 to 8 carbon atoms (such as methyl, ethyl, n-propyl, n-pentyl, isobutyl), an alkenyl group having 3 to 8 carbon atoms (such as 3-butenyl, 2-propenyl), and an aralkyl group having 7 to 10 carbon atoms (such as benzyl, phenethyl). The aryl group represented by R41, R42 , R43, R44, R45, R46, R47, or R48 include, for example, a phenyl group and the heterocyclic group include, for example, pyridyl group (e.g., 2- or 4-pyridyl), pyrazyl group, furyl group (e.g., 2-furyl), thienyl group (e.g., 2-thienyl), sulforanyl group, tetrahydrofuryl group, piperidyl group, pyrrolyl group, and imidazolyl group. R41, R42, R43, R44, R45, R46, R47, or R48 each may be substituted and examples of the substituent group include a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), an alkoxy group (e.g., methoxy, ethoxy), an aryloxy group (e.g., phenoxy, p-tolyoxy), cyano group, a carbamoyl group (e.g., carbamoyl, N-methylcarbamoyl, N,N-tetramethylenecarbamoyl), a sulfamoyl group (e.g., sulfamoyl, N,N-3-oxapentamethyleneaminosulfonyl), a methanesulfonyl group, an alkoxycarbonyl group (e.g., ethoxycarbonyl, butoxycarbonyl), an aryl group (e.g., phenyl, carboxyphenyl), and an acyl group (e.g., acetyl, benzoyl). Exemplary examples of the aliphatic group containing an aqueous solubility promoting group include carboxymethyl, sulfoethyl, sulfopropyl, sulfobutyl, sulfopentyl, 3-sulfobutyl, 6-sulfo-3-oxahexyl, xcfx89-sulfopropoxycarbonylmethyl, xcfx89-sulfopropylaminocarbonyl-methyl, N-ethyl-N-sulfopropyl, 3-sulfinobutyl, 3-phosphonopropyl, 4-sulfo-3-butenyl, 2-carboxy-2propenyl, o-sulfobenzyl, p-sulfophenethyl, and p-carboxybenzyl. Examples of the aryl group containing an aqueous solubility promoting group include p-sulfophenyl and p-carboxyphenyl; and examples of the heterocyclic group containing an aqueous solubility promoting group include 4-sulfothienyl and 3-carboxypyridyl. Of these, it is preferred that R41 and R45 are a sulfo-substituted alkyl group, and at least two of R42, R43, R44, R46, R47 and R28 are carboxymethyl.
Z41 and Z42 each represent a 5- or 6-membered nitrogen-containing heterocyclic group. The nitrogen-containing heterocyclic rings include basic nitrogen-containing heterocyclic rings forming a cyanine dye, such as an oxazole ring (e.g., oxazole, benzoxazole, naphthoxazole), a thiazole ring (e.g., thiazolidine, thiazole, benzthiazole, naphthothiazole), an imidazole ring (e.g., imidazole, benzimidazole, naphthoimidazole), a selenazole ring (e.g., selenazole, benzoselenazole, naphthoselenazole), a tetrazole ring (e.g., tetrazole, benztetrazole, naphthotetrazole), a pyrydine ring (e.g., pyridine quinoline), and pyrrole ring (e.g., pyrrole, indole, indolenine). The nitrogen-containing heterocyclic group represented by Z21 or Z22 may be substituted at any position on the heterocyclic ring.
Examples of the substituent group include a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom9, trifluoromethyl, an alkoxy group (e.g., unsubstituted alkoxy such as methoxy, ethoxy and butoxy, and substituted alkoxy such as 2-methoxyethoxy and benzoyloxy), hydroxy, cyano, an aryloxy group (e.g., phenoxy, tolyloxy), an aryl group (e.g., phenyl, p-chlorophenyl, p-tolyl, p-methoxyphenyl), styryl group, a heterocyclic group (e.g., furyl, thienyl9, a carbamoyl group (e.g., carbamoyl, N-ethylcarbamoyl), a sulfamoyl group (e.g., sulfamoyl, N,N-dimethylsulfamoyl), an acylamino group (e.g., acetylamino, propionylamino, benzoylamino), an acyl group (e.g., acetyl, benzoyl), an alkoxycarbonyl group (e.g., ethoxycarbonyl), a sulfonamido group (e.g., methanesulfonamido, p-toluenesulfonamido), carboxy group, and an alkyl group (e.g., methyl, ethyl, isopropyl).
L41, L42, L43, L44, L45, L46, L47 and L48 represent an unsubstituted or substituted methine group. The substituent group thereof include, for example, an alky group (e.g., methyl, ethyl), a pahenyl group (e.g., phenyl, carboxyphenyl), an alkoxy group (e.g., methoxy, ethoxy), an aryloxy group (e.g., phenoxy, carboxyphenoxy), an aralkyl group (e.g., benzyl) and a fluorine atom. The sensitizing dye of the invention, in which either one of L41, L42, L43, L44, L45, L46, L47 and L48 is a substituted methine group achieves higher spectral sensitivity and exhibits characteristics such that a dye is easily bleached in a processing solution, advantageously leading to reduced dye staining.
W41 and W42 represent a oxygen atom, sulfur atom, =C less than (E41)(E42) or =C less than  less than (E43) (E44), in which E41, E42, E43 and E44 each represent an electron-withdrawing group, which may combine with each other to form an oxo-group containing heterocyclic ring or an acidic heterocyclic ring.
141 represents 0 or 1; M21 and M22 represent a cation or an acid anion. Examples of the cation include proton, organic ammonium ion (e.g., triethylammonium, triethanolammonium), inorganic cations (e.g., lithium, sodium or calcium ion). Examples of the acid anion include a halide ion (e.g., chloride ion, bromide ion, iodide ion), p-toluenesulfonate ion, perchlorate ion, and 4-fluoroborate ion. n41 and n42 represent the number of ion(s) forming an intramolecular salt and counterbalancing the total intramolecular charge.
The electron-withdrawing group represented by E41, E42, E43 and E44 is selected from the groups exhibiting a Hammett "sgr"p value of 0.3 or more, and examples thereof include cyano group, a carbamoyl group (e.g., carbamoyl, morpholinocarbamoyl, N-methylcarbamoyl), an alkoxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl), a sulfamoyl group (e.g., sulfamoyl, morpholinosulfonyl, N,N-dimethylsulfamoyl), an acyl group (e.g., acetyl, benzoyl), and a sulfonyl group (e.g., methanesulfonyl, ethanesulfonyl, benzenesulfonyl, toluenesulfonyl). The oxo-group containing heterocyclic ring and an acidic heterocyclic ring formed by E41, E42, E43 and E44 are the same as defined in E21 and E22.
Ra and Rb each represent a lower alkyl group, an aryl group or a heterocyclic group. The lower alkyl group include substituted and unsubstituted ones, for example, methyl, ethyl, propyl, 2-hydroxyethyl, 2-methoxyethyl, trifluoromethyl, carboxymethyl, carboxymethyl, 2-sulfoethyl and benzyl. The aryl group and heterocyclic group represented by Ra and Rb include the same as defined in R42, R43, R44, R46, R47 and R48.
Examples of the spectral sensitizing dyes represented by formula (3-a) or (3-b) are shown below but are by no means limited to these compounds. 
The spectral sensitizing dyes represented by formula (4) will be described.
In formula (4), the aqueous solubility promoting group contained in R51, R52, R53 or R54 include, for example, a sulfo group, a carboxy group, a phosphono group, a sulfate group and a sulfino group. The aliphatic group represented by R51, R52, R53 or R54 include, for example, a straight or branched alkyl group having 1 to 8 carbon atoms (such as methyl, ethyl, n-propyl, n-pentyl, isobutyl), an alkenyl group having 3 to 8 carbon atoms (such as 3-butenyl, 2-propenyl), and an aralkyl group having 7 to 10 carbon atoms (such as benzyl, phenethyl). The aryl group represented by R51, R52, R53 or R54 include, for example, a phenyl group and the heterocyclic group include, for example, pyridyl group (e.g., 2- or 4-pyridyl), pyrazyl group, furyl group (e.g., 2-furyl), thienyl group (e.g., 2-thienyl), sulforanyl group, tetrahydrofuryl group, piperidyl group, pyrrolyl group, and imidazolyl group. R51, R52, R53 or R54 each may be substituted and examples of the substituent group include a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), an alkoxy group (e.g., methoxy, ethoxy), an aryloxy group (e.g., phenoxy, p-tolyoxy), cyano group, a carbamoyl group (e.g., carbamoyl, N-methylcarbamoyl, N,N-tetramethylenecarbamoyl), a sulfamoyl group (e.g., sulfamoyl, N,N-3-oxapentamethyleneaminosulfonyl), a methanesulfonyl group, an alkoxycarbonyl group (e.g., ethoxycarbonyl, butoxycarbonyl), an aryl group (e.g., phenyl, carboxyphenyl), and an acyl group (e.g., acetyl, benzoyl). Exemplary examples of the aliphatic group containing an aqueous solubility promoting group include carboxymethyl, sulfoethyl, sulfopropyl, sulfobutyl, sulfopentyl, 3-sulfobutyl, 6-sulfo-3-oxahexyl, xcfx89-sulfopropoxycarbonylmethyl, xcfx89-sulfopropylaminocarbonyl-methyl, N-ethyl-N-sulfopropyl, 3-sulfinobutyl, 3-phosphonopropyl, 4-sulfo-3-butenyl, 2-carboxy-2propenyl, o-sulfobenzyl, p-sulfophenethyl, and p-carboxybenzyl. Examples of the aryl group containing an aqueous solubility promoting group include p-sulfophenyl and p-carboxyphenyl; and examples of the heterocyclic group containing an aqueous solubility promoting group include 4-sulfothienyl and 3-carboxypyridyl. Of these, it is preferred that R21 and R25 are a sulfo group containing alkyl group, and at least two of R51, R52, R53 or R54 are carboxymethyl.
The alkyl group represented by V51 and V52 include straight or branched alkyl groups, such as methyl, ethyl, isopropyl, t-butyl, iso-butyl, t-pentyl and hexyl. The alkoxy group represented by V51 and V52 include, for example, methoxy, ethoxy, and propoxy. The aryl group represented by V51 and V52, which may be substituted at any position include, for example, phenyl, p-tolyl, p-hydroxyphenyl, and p-methoxyphenyl. The condensed azole ring formed by the combination of V31 and V32 include, for example, 4,5,6,7-tetrahydrobenzoxazole, naphtha[1,2-d]oxazole, naphtha[2,3-d]oxazole, benzothiazole, 4,5,6,7-tetrahydrobenzothiazole, naphtha[1,2-d]thiazole, naphtha[2,3-d]thiazole, benzoselenazole and naphtha[1,2-d]selenazole. The group represented by V31 and V32 or the condensed ring formed by V31 and V32 may be substituted by a substituent group at any position thereof. Examples of the substituent group include a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom9, trifluoromethyl, an alkoxy group (e.g., unsubstituted alkoxy such as methoxy, ethoxy and butoxy, and substituted alkoxy such as 2-methoxyethoxy and benzoyloxy), hydroxy, cyano, an aryloxy group (e.g., phenoxy, tolyloxy), an aryl group (e.g., phenyl, p-chlorophenyl, p-tolyl, p-methoxyphenyl), styryl group, a heterocyclic group (e.g., furyl, thienyl9, a carbamoyl group (e.g., carbamoyl, N-ethylcarbamoyl), a sulfamoyl group (e.g., sulfamoyl, N,N-dimethylsulfamoyl), an acylamino group (e.g., acetylamino, propionylamino, benzoylamino), an acyl group (e.g., acetyl, benzoyl), an alkoxycarbonyl group (e.g., ethoxycarbonyl), a sulfonamido group (e.g., methanesulfonamido, p-toluenesulfonamido), carboxy group, and an alkyl group (e.g., methyl, ethyl, isopropyl).
L51 and L52 represent an unsubstituted or substituted methine group. The substituent group thereof include, for example, an alky group (e.g., methyl, ethyl), a pahenyl group (e.g., phenyl, carboxyphenyl), an alkoxy group (e.g., methoxy), an aralkyl group (e.g., benzyl) and a fluorine atom.
E51 and E52 represent an electron-withdrawing group, which may combine with each other to form an oxo-group containing heterocyclic ring or an acidic heterocyclic ring.
The sensitizing dye of the invention, in which either L51 or L52 is a substituted methine group achieves higher spectral sensitivity and exhibits characteristics such that a dye is easily bleached in a processing solution, advantageously leading to reduced dye staining.
W51 represents a oxygen atom, sulfur atom, or =C less than (E51) (E22), in which E51 and E52 each represent an electron-withdrawing group. The electron-withdrawing group represented by E51 and E52 is selected from the groups exhibiting a Hammett "sgr"p value of 0.3 or more, and examples thereof include cyano group, a carbamoyl group (e.g., carbamoyl, morpholinocarbamoyl, N-methylcarbamoyl), an alkoxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl), a sulfamoyl group (e.g., sulfamoyl, morpholinosulfonyl, N,N-dimethylsulfamoyl), an acyl group (e.g., acetyl, benzoyl), and a sulfonyl group (e.g., methanesulfonyl, ethanesulfonyl, benzenesulfonyl, toluenesulfonyl). The oxo-group containing heterocyclic ring and an acidic heterocyclic ring formed by E51 and E52 are the same as defined in E21 and E22.
The heterocyclic group is the same as defined in R51, R52, R53 and R54.
M51 represents a cation or an acid anion. Examples of the cation include proton, organic ammonium ion (e.g., triethylammonium, triethanolammonium), inorganic cations (e.g., lithium, sodium or calcium ion). Examples of the acid anion include a halide ion (e.g., chloride ion, bromide ion, iodide ion), p-toluenesulfonate ion, perchlorate ion, and 4-fluoroborate ion. n41 and n42 represent the number of ion(s) forming an intramolecular salt and counterbalancing the total intramolecular charge.
Examples of the spectral sensitizing dyes represented by formula (4) are shown below but are by no means limited to these compounds. 
The foregoing compounds can be readily synthesized according the commonly known methods, as described in F. M. Hamer xe2x80x9cCyanine Dyes and Related Compoundsxe2x80x9d (Interscience Publishers, 1964), U.S. Pat. Nos. 2,454,629 and 2,493,748; British Patent No. 489,335 and European Patent No. 730,008.
The spectral sensitizing dyes represented by formula (5) will be described. R61 and R62 represent an alkyl group containing an aqueous solubility promoting group, which may be in a free form or a salt form. The solubility herewith means that the sensitizing dye represented by formula (5) dissolves in water at room temperature in an amount of 0.5 g or more per 1 lit. of water. Examples of R61 and R62 are as follows: 
wherein Q63 represents a bivalent linkage group including an alkylene group, an arylenes group and an alkenylene group. M61 represents a hydrogen atom, ammonium, alkali metal (e.g., sodium, potassium), alkaline earth metal (e/.g., cakcium), or organic amines (e.g., triethylamine salt, 1,8-diazabicyclo[5,4,0]-7-undecene salt). R60 represents an alkyl group or an aryl group. Q63 is preferably an alkylene group having 1 to 20 carbon atoms (e.g., methylene, ethylene, propylene, butylenes, pentylene), an arylenes group having 6 to 20 carbon atoms (e/g/. phenylene), an alkenylene group having 2 to 20 carbon atoms (e.g., propenylene) or a bivalent group formed by combination of the foregoing groups. These bivalent linkage group may contain a group selected from the group of xe2x80x94NHCOxe2x80x94, xe2x80x94COOxe2x80x94, xe2x80x94NHSO2xe2x80x94, xe2x80x94SO2Oxe2x80x94, xe2x80x94NHCONHxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94SOxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94COxe2x80x94, and xe2x80x94NHxe2x80x94. Exemplary examples of Q63 are described below: 
In addition, there can also be employed linkage groups described in European Patent No. 472,004, page 5 to 7. Q63 is more preferanly an alkylene group having 1 to 10 carbon atoms, phenylene group or combination thereof, and still more preferably methylene, ethylene, propylene or butylenes.
R60 is preferably an alkyl group having 1 to 10 carbon atoms (e.g., methyl, ethyl, hydroxyethyl) or an aryl group having 6 to 12 carbon atoms (e.g., phenyl, 4-chlorophenyl).
V61, V62, V63 and V64 represent a hydrogen atom or univalent group, and preferably a hydrogen atom, a unsubstituted alkyl group (preferably having 1 to 3 carbon atoms, such as methyl, ethyl, propyl), a substituted alkyl group (preferably having 1 to 2 carbon atoms, such as hydroxymethyl), an alkoxy group (preferably having 1 to 3 carbon atoms, such as methoxy, ethoxy), a fluorine atom, chlorine atom, hydroxy, an acetyl group, a carbamoyl group or cyano. V61, V62, V63 and V64 are more preferably a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, hydroxymethyl, acetyl group, fluorine atom or chlorine atom, still more preferably a hydrogen atom, methyl or methoxy, and most preferably a hydrogen atom. The total of molecular weights of V61, V62, V63 and V64 is 4 to 50. The total of the molecular weights of V61, V62, V63 and V64 refers to the total sum of each molecular weight of V61, V62, V63 or V64. In the case of V61=V62=V63=V64 hydrogen atom, for example, the total molecular weight id 4; and in the cases where V61=V62=V63=hydrogen atom and V64 is a phenyl group, the total molecular weight is 77. The total molecular weight is preferably 4 to 35, more preferably 4 to 21, and still more preferably 4.
L61, L62, L63 and L64 represent a methine group or a substituted methine group, in which examples of substituent group include substituted or unsubstituted alkyl group (preferably having 1 to 5 carbon atoms, e.g., methyl, ethyl, n-propyl, I-propyl, cyclopropyl, butyl, 2-carboxyethyl, etc.), substituted or unsubstituted aryl group (preferably having 6 to 12 carbon atoms, e.g., phenyl, naphthyl, anthryl, o-carboxyphenyl, etc.), a heterocyclic group (a heterocyclic ring of which is preferably a 3- to 7-membered heterocyclic ring comprising 2 to 12 carbon atoms and heteroatoms selected from S,, N, and Se, e.g., pyridine, thienyl, furan, barbituric acid), a halogen atom (e.g., chlorine, bromine, iodine atoms), an alkoxy group (preferably having 1 to 5 carbon atoms, e.g., methoxy, ethoxy), a substituted or unsubstituted amino group (preferably having 0 to 12 carbon atoms, e.g., N,N-diphenylamino, N-methyl-N-phenylamino, N-methylpyradino), and an alkylthio group (preferably 1 to 5 carbon atoms, e.g., methylthio, ethylthio). The methine group may combine with another methine group to form a ring (preferably 5- to 7-membered ring such as cyclohexene ring) or an auxochrome (e.g., benzoxazole ring). L61, L62 and L64 are preferably a unsubstituted methine group. L63 is preferably a methine group substituted with an unsubstituted alkyl group (e.g., methyl, ethyl).
M61 is a cation or an anion necessary to counterbalance the total intramolecular charge, and n61 represents the number of ion(s) necessary to counterbalance the total intramolecular charge. Example of cations include hydrohen ion, inorganic ammonium ion, organic ammonium ion (e.g., tetraalkylammonium ion, pyridinium ion), alkali metl ion, (e.g., sodium ion, potassium ion), and alkaline earth metal ion (e.g., calcium ion). Examples of anions include inorganic anions (e.g., fluoride ion, chloride ion, bromide ion, iodide ion), substituted arysulfonate ions (e.g., p-toluenesulfonate ion, p-chlorobenzenesulfonate ion), an arysulfonate ion (e.g., 1,3-benzene-disulfonate ion, 2,6-naphthalene-disulfonate ion), alkylsulfate ions (e.g., methylsulfate ion, ethylsulfate ion), sulfate ion, thicyanate ion, perchlorate ion, tetrafluoroborate ion, picrinate ion, acetate ion and trifluoromethansulfonate ion. Further, as a charge-balamcing counterion, an ionic polymer a compound (spectral sensitizing dye) having a charge opposite to the charge of the compound of formula (5) may be used.metal complex ions such as bisbenzene-1,2-dithiolate nickel (III) are also usable. Of these, cations such as ammonium ion (e.g., triethylamine salt, 1,8-diazacyclo[5,4,0]-7-undecene), and alkali metal ions (e.g., sodium ion, potassium ion) is preferred; alkali metal ions (e.g., sodium ion, potassium ion) is more preferred; and sodium ion is still more preferred.
The sensitizing dye represented by formula (5) is preferably a sensitizing dye represented by the following formula (5-a): 
wherein Q71 and Q72 represent an alkylene group, V71, V72, V73 and V74 each represent a hydrogen atom, methyl, ethyl, hydroxy, an acetyl group, fluorine atom or chlorine atom. Total sum of molecular weights of V71, V72, V73 and V74 is 4 to 50; M71 is a charge-balancing counter ion and m71 is an integer of 0 to 4. In formula (5-a), V71, V72, V73 and V74 are each preferably a hydrogen atom.
Specifically, Q71 and Q72 is preferably alkylene group (preferably having 1 to 8 carbon atom, and more preferably 1 to 4 carbon atoms, such as methylene, ethylene, propylene, n-butylene, I-butylene). Q71 is more preferably an ethylene group and Q72 is more preferably a methylene group. It is more preferred that Q71 is an ethylene group and Q72 is a methylene group, Examples of M71 are the same as cited in M61. Preferred M61 is the the as cited in M61, and sodium ion is more preferred.
Examples of spectral sensitizing dyes represented by formula (5) are shown below, but are by no means limited to these.
The foregoing sensitizing dyes represented by formula (5) can be readily synthesized according the commonly known methods, as described in F. M. Hamer xe2x80x9cCyanine Dyes and Related Compoundsxe2x80x9d (Interscience Publishers, 1964); D. S. Sturmer xe2x80x9cHeterocyclic Compounds-Special Topics in Heterocyclic chemistryxe2x80x9d chapt. 18, sect. 14, page 482-515 (John-Wirey and Sons, 1977); xe2x80x9cRodd7s Chemistry of Carbon Compoundxe2x80x9d (2nd Ed., vol. IV, part B. 1985) chapt. 15, page 369-422 and (2nd Ed., vol IV, part B) chapt. 15, page 267-296 (Elservier Science Publishing Company Inc.).
The adding amount of the sensitizing dye represented by formula (1-a), formula (1-b), formula (3-a), formula (3-b), formula (4) or formula (5), depending on the conditions to be used and the kind of emulsions, is preferably 1xc3x9710xe2x88x926 to 5xc3x9710xe2x88x923, and more preferably 2xc3x9710xe2x88x926 to 2xc3x9710xe2x88x923 mol per mol of silver halide. The sensitizing dye represented by formula (1-a), formula (1-b), formula (3-a), formula (3-b), formula (4) or formula (5) can be incorporated into silver halide emulsions by the commonly known methods. Examples thereof include incorporation through protonating dissolution described in JP-A Nos. 50-80826 and 50-80827; incorporation through dispersion with a surfactant described in U.S. Pat. No. 3,822,135 and JP-A No. 50-11419; incorporation through dispersion in a hydrophilic substrate described in U.S. Pat. Nos. 3,676,147, 3,469,987, 4,247,627 and JP-A Nos. 51-59942, 53-16624, 53-102732, 53-102733 and 53-137131; incorporation in the form of a solid solution described East German Patent No. 143,324; and incorporation by dissolving the dye in an aqueous soluble solvent (e.g., water, or low boiling solvent such as methanol, ethanol, propyl alcohol, acetone, or fluorinated alcohol, or a high boiling solvent such as dimethyl formamide, methyl cellosolve or phenyl cellosolve), as described in Research Disclosure No. 21802, JP-B No. 50-40659 and JP-A 59-148053. The sensitizing dye represented by formula (1-a), formula (1-b), formula (3-a), formula (3-b), formula (4) or formula (5) may added at any stage of the process of emulsion making, i.e., of physical ripening to chemical ripening and coating but it is preferred to add after starting physical ripening and before completing chemical ripening. It is specifically preferred to add the dye during physical ripening or prior to addition of a chemical sensitizer during chemical ripening, or immediately after adding a chemical sensitizer to enhance effects of this invention. The sensitizing dye represented by formula (1-a), formula (1-b), formula (3-a), formula (3-b), formula (4) or formula (5) may be used in combination with other sensitizing dye(s). In such a case, the sensitizing dyes may be added simultaneously or separately.
The sensitizing dye of the invention can achieve further enhanced spectral sensitivity by the use of a compound exhibiting a super-sensitizing effect, in combination. Examples of the compound exhibiting the super-sensitizing effectcompounds containing a pyrimidinylamino group or triazinylamino group, described in U.S. Pat. Nos. 2,933,390, 3,416,927, 3,511,664, 3,615,613, 3,615,632 and 3,635,721, JP-A 3-15042, 3-110545 and 4-255841; aromatic organic formaldehyde condensates described in British Patent No. 1,137,580 and JP-A 61-169833; carix-arene derivatives described in JP-A 4-184332; halogenated benzotriazole derivatives described in U.S. Pat. No. 4,030,927; bis-pyridinium compounds described in JP-A No. 59-142541 and 59-188641; aromatic heterocyclic quaternary salt compounds described in JP-A 59-191032; electron-donating compounds described in JP-A 60-79348; a polymer containing an aminoallylidene malononitrile unit described in U.S. Pat. No. 4,307,183; hydroxytetrazaindene derivatives described in JP-A 4-149937; 1,3-oxadiazole derivatives described in U.S. Pat. No. 3,615,633; and amino-1,2,3,4-thiatriazole derivatives described in U.S. Pat. No. 4,780,404. The time for adding these super-sensitizers is not specifically limited and the compound may be added at any time. The supersensitizer is incorporated in an amount of 1xc3x9710xe2x88x926 to 1xc3x9710xe2x88x921 mole per mole of silver halide. The ratio of supersensitizer to sensitizing dye is within the range of 1/10 to 10/1.
Photographic materials according to this invention are suitable for use in printing plate making, exhibiting high contrast and forming high contrast images. In the photographic material of the invention, hydrazine derivatives are preferably employed as a contrast-increasing agent. When the photographic material of this invention is exposed and processed, the slope (xcex3) on the characteristic curve within the density rage of 1 .0 to 3.0 of the formed images is preferably 10 to 100. To achieve the xcex3 of 10 to 100, it is preferred to allow a contrast-increasing agent to be contained in the photographic material. Employed as a contrast-increasing agent are hydrazine derivatives and 5- or 6-membered nitrogen-containing heterocyclic derivative, tetrazolium compounds described in JP-A No. 10-10680.
The hydrazine derivative is preferably represented by the following formula (H): 
wherein A is an aryl group or a heterocyclic group containing an oxygen atom or a sulfur atom; G is xe2x80x94(CO)nxe2x80x94, sulfonyl group, sulfoxy group, xe2x80x94P(=O)R2xe2x80x94, or iminomethylene group, and n is an integer of 1 or 2, in which R2 is a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkenyloxy, substituted or unsubstituted alkynyloxy, substituted or unsubstituted aryloxy or substituted or unsubstituted amino group; A1 and A2 are both hydrogen atoms, or either of them is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group or a substituted or unsubstituted acyl group; R is a hydrogen atom or a substituted or unsubstituted alkyl, alkenyl, aryl, alkoxy, alkenyloxy, aryloxy, heterocyclic-oxy, amino or carbamoyl group or oxycarbonyl group.
Of the compounds represented by formula (H), a compound represented by the following formula (Ha) is preferred: 
wherein R11 is an aliphatic group (e.g., octyl, decyl), an aromatic group (e.g., phenyl, 2-hydroxyphenyl, chlorophenyl), or a heterocyclic group (e.g., pyridyl, thienyl, furyl), each of which may be substituted. Specifically, R11 having a ballast group or a group promoting adsorption onto silver halide is preferred. The ballast group is preferably one which are commonly used in non-diffusible photographic additives such as couplers, and having 8 or less carbon atoms, such as alkyl, alkenyl, alkynyl, alkoxy, phenyl and alkylphenoxy. Examples of the group promoting adsorption onto silver halide include a thiourea group, a thiourethane group, mercapto group, a thioether group, a heterocyclic group, a thioamino-heterocyclic group, a mercapto-heterocyclic group and adsorbing groups described in JP-A 64-90439. In formula (Ha), X1 is a group capable of being substituted on a phenyl group; m is an integer of 0 to 4, provided that when m is 2 or more, X may be the same or different. In formula (Ha), A3 and A4 are the same as defined in A1 and A2 of formula (H) and are preferably both hydrogen atoms. In formula (Ha), G is a carbonyl group, oxalyl group, sulfonyl group, sulfoxy group, phosphoryl or imonomethylene group; and is preferably a carbonyl group. In formula (Ha), R12 is a hydrogen atom, or a substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl or heterocyclic group, hydroxy, a substituted or unsubstituted amino, carbamoyl or oxycarbonyl group; specifically, R12 is preferably a substituted alkyl group, in which the carbon atom attached to G is attached to an electron-withdrawing group, xe2x80x94COOR13 or xe2x80x94CON(R14) (R15), in which R13 is an alkynyl group or a saturated heterocyclic group, R14 is a hydrogen atom, an alkyl group, an alkenyl group, alkynyl group, aryl group or a heterocyclic group; and R15 is an alkenyl group, an alkynyl group, a saturated heterocyclic group, hydroxy, or an alkoxy group. R12 is more preferably a substituted alkyl group, in which the carbon atom attached to G is attached to two electron-withdrawing groups (still more preferably three electron-withdrawing groups). The electron-withdrawing group attached to the carbon atom of R12, which is attached to G, is preferably one which has a "sgr"p of 0.2 or more and "sgr"m of 0.3 or more (in which "sgr"p and "sgr"m are each a Hammett""s substitution constant). Examples thereof include halogen, cyano, nitro, nitroso, polyhaloalkyl group, polyhaloaryl group, alkyl- or aryl-carbonyl group, formyl, alkyl- or aryl-oxycarbonyl group, alkylcarbonyloxy group, carbamoyl group, alkyl- or aryl-sulfinyl group, alkyl- or aryl-sulfonyl group, alkyl- or aryl-sulfonyloxy group, sulfamoyl group, phosphine group, phosphineoxide group, phosphone ester group, phosphoneamido group, arylazo group, amidino group, ammonoi group, sulfonoi group, and electron-deficient heterocyclic group. In formula (Ha), R12 is specifically preferably a fluorine-substituted alkyl group, such as monofluoromethyl, difluoromethyl and trifluoromethyl.
Exemplary examples of the compounds represented by formula (H) are shown below, but are not limited to these. 
As other specific examples of hydrazine compounds, for example, those Exemplified Compounds (1) through (252) disclosed on columns 4 through 60 of U.S. Pat. No. 5,229,248 can be mentioned.
The hydrazine compounds according to the present invention can be synthesized according to the conventionally known methods in the art. For example, they may be synthesized according to the method disclosed on columns 59 through 80 in the U.S. Pat. No. 5,229,248.
An adding amount of the hydrazine derivative may be optional if it is one capable of hardening the light-sensitive photographic material according to the present invention, and the optimum amount of addition may be varied depending on the grain size of the silver halide particles, halide composition, degree of chemical ripening and kind of restraining agent, etc.; however, it is generally between 10xe2x88x926 and 10xe2x88x921 mol, and, more preferably, between 10xe2x88x925 and 10xe2x88x922 mol per one mol of silver halide. Hydrazine compounds are incorporated into at least a layer on emulsion-side, preferably a silver halide emulsion layer and/or its adjacent layer, and more preferably a silver halide emulsion layer. The hydrazine content in a layer closest to the support among hydrazine-containing layer(s) is preferably 0.2 to 0.8 mol equivalent, and more preferably 0.4 to 0.6 mol equivalent, based on the total hydrazine content in the whole photographic component layers. The hydrazine compounds are used alone or in combination.
In cases where the photographic material to be processed contains the nucleating agent described above, it is preferred to use a nucleation-promoting agent. Examples thereof include exemplary compounds (2-1) through (2-1) described in JP-A 6-258751, compounds (3-1) through (3-6) described in JP-A 6-258751, onium compounds described in JP-A 7-270957, compounds represented by general formula I described in JP-A 7-104420, and thiosulfonic acid compounds described in JP-A 2-103536, page 17, right lower column line 19 to page 18, right upper column, line 4, and page 18, lower right column line 1-5, and JP-A 1-237538. The nucleation-promoting agent may be incorporated into any layer of photographic component layers on emulsion-side, and preferably into a silver halide emulsion layer or its adjacent layer. The amount to be incorporated, depending of the grain size, halide composition, the extent of chemical sensitization of silver halide grains and the kind of a restraining agent, is preferably 10xe2x88x926 to 10xe2x88x921 mol, and more preferably 10xe2x88x925 to 10xe2x88x922 mol per mol of silver halide.
The compound represented by formula (A) will be described.
In formula (A), R1 and R2 are each a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkylthio group, provided that R1 and R2 may combine together with each other to form a ring.
In formula (A), R1 and R2 combine together with each other to form a ring, and the resulting compound represented by the following formula (A-a) is specifically preferred: 
wherein R3 is a hydrogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted amino group, substituted or unsubstituted alkoxy group, sulfo group, carboxy group, amido group or sulfonamido group; Y1 is O or S; Y2 is O, S or NR4, in which R4 is substituted or unsubstituted alkyl group or substituted or unsubstituted aryl group; and M1 and M2 each are a hydrogen atom or alkali metal atom.
As the alkyl group of formula (A) and formula (A-a) is preferred a lower alkyl group, such as an alkyl group having 1 to 5 carbon atoms; the amino group is preferably unsubstituted amino group or amino group substituted by a lower alkoxy group; the alkoxy group is preferably a lower alkoxy group; the aryl group is preferably a phenyl group or naphthyl group. The foregoing groups may be substituted and examples of preferred substituent groups include a hydroxy group, halogen atom, alkoxy group, sulfo group, carboxy group, amido group, and sulfonamido group. M1 and M2 each are a hydrogen atom or alkali metal atom, preferably sodium or potassium atom.
Exemplary examples of the compound represented by formulas A) and (A-a) are shown below, but the compounds are not limited thereto.
The content of the compound represented by formula (A) or (A-a) in a developer solution is preferably 20 to 120 g/l.
Of these compounds, representative ones are ascorbic acid, erythorbic acid or salts thereof (e.g., sodium, potassium, lithium etc.), derivatives derived therefrom, which are commercially available and readily synthesized by well known methods.
The developing agent represented by formula (A) is used preferably in combination with a developing agent such as 3-pyrazolidones (e.g., 1-phenyl-3-pyrazolidne, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone), aminophenols (e.g., o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methylp-aminophenol, 2,4-diaminophenol) or hydrophilic group-substituted dihydroxybenzenes (e.g., hydroquinone monosulfonate, sodium hydroquinonemonosulfonate, potassium 2,5-hydroquinone-disulfonate). Specifically, a combination of ascorbic acid or its derivatives and 3-pyrazolidones, or a combination of ascorbic acid or its derivatives, 3-pyrazolidones and dihydroxybebzenes substituted with a hydrophilic group is preferred. In cases where used in combination, developing agents such as 3-pyrazolidones, aminophenols or hydrophilic group-substituted dihydroxybebzenes are used preferably in an amount of not less than 0.01 mole and less than 0.2 mole per lit. of developing solution.
Commonly known various types of light sources are employed in the processing method of silver halide photographic materials in this invention. For example, there are employed laser light sources such as Hexe2x80x94Ne laser, LED, infrared semiconductor laser, red semiconductor laser and Ar laser. Specifically, extremely short period exposure resulted in marked effects of this invention.
Halide composition of silver halide grains contained in a silver halide emulsion of the photographic material is not specifically limited. In cases where subjected to processing at a low replenishing rate or subjected to rapid processing, a silver halide emulsion is preferred, comprising silver chloride, silver bromochloride containing 50 to 1000 mol % chloride or silver iodobromochloride containing 60 to 90 mol % chloride.
The average grain size of the silver halide is preferably 1.2 xcexcm or less, and, more preferably 0.1 to 0.3 xcexcm. The term xe2x80x9caverage grain sizexe2x80x9d has been used commonly in the art. The term xe2x80x9cgrain sizexe2x80x9d usually refers to a diameter of the grain, when the grain is of spherical shape or in the form close thereto. In the case when the grain is a cubic shape, it means a diameter of a sphere when the cube is converted into a sphere having the equivalent volume. With regard to the method of obtaining the average diameter, one can refer to the disclosure on pages 36-43, third edition of C. E. K. Mees and T. H. James xe2x80x9cThe theory of the Photographic Processxe2x80x9d, pages 36-43, Macmillan Co. (1966).
There is no limitation as to the shape of the silver halide grain, and any one of tabular, cubic, spherical, tetradecahedral or octahedral shape can optionally be used. Concerning grain size distribution, the narrower, the more preferable. Particularly, so-called mono-dispersed emulsion, in which not less than 90%, preferably, 95% of the total number of grains fall within the range of the average grain size +40%, is preferable.
The type of reaction of a soluble silver salt with soluble halide in the preparation of a silver halide emulsion may be normal precipitation, double jet precipitation or combination thereof. A method of forming grains in the presence of silver ions in excess (so-called, reversed precipitation) may be applicable. As one of the double jet precipitation, there is used a controlled double jet method in which the pAg of liquid phase is maintained at a given value during the course of grain formation. According to this method, there can be obtained a silver halide emulsion comprised of monodisperse grains with regular crystal form.
At the time of physical ripening or chemical ripening, metal salts of zinc, lead, thallium, iridium, rhodium, ruthenium, osmium, palladium, platinum, etc. can be coexisted. It is often commonly used to incorporate 10xe2x88x928-10xe2x88x923 of iridium per mol silver halide for the purpose of improving high intensity reciprocity law failure characteristics. In the present invention, in order to obtain an emulsion with high contrast, it is preferable for 10xe2x88x929 to 10xe2x88x923 mol of rhodium, ruthenium, osmium and/or rhenium per mol of silver halide to be incorporated in the silver halide emulsion.
A metal compound may be added in the form of a complex salt, in which the metal is coordinate with a halogen, carbonyl, nitrocyl, thionitrocyl, amine, cyan, thiocyan, ammonia, tellurocyl, selenocyan, dipyridyl, tripyridyl, phenanthroline or a combination thereof. The oxidation state of the metal may be optionally selected within the range of the minimum level to the maximum level. As preferred ligands are cited hexa-dentated ligands described in JP-A 2-2082, 2-20853, 2-20854 and 2-20855; alkali metal salts include a sodium salt, potassium salt and cesium salt and primary secondary and tertiary amines are also cited. A transition metal complex salt may be formed in the form of an aquo-complex. Examples thereof include K2[RuCl6], (NH4)2[RuCl6], K2 Ru(NOCl4(SCN)), and K2[RuCl5(H2O)]. Ru may be replaced by Rh, Os, Re, Ir, Pd or Pt. It is preferable that rhodium, ruthenium, osmium and/or rhenium compound is added during the time of forming silver halide grains. Addition thereof may be optional, including a method of distributing uniformly inside the grain and a method of localizing in the core or shell portion of core/shell-structure grains. Often, better results are obtained in the case when they are made present in the shell portion. Further, in the case when they are made present in a discrete layer structure, a method in which amount of presence is made greater depending on the distance from the center of the grain, may also be applied. Amount of addition may optionally be selected from the range between 10xe2x88x929 and 10xe2x88x923 mol per mol of silver halide.
Silver halide emulsions and preparation methods thereof are referred to Research Disclosure 17643 pages 22-23 (December 1973) and the references referred therein.
The silver halide emulsion used in the present invention may or may not be chemically sensitized. As method of chemical sensitization, sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization and noble metal sensitization have been well known in the art, and these methods may be used either singly or in combination. As a sulfur sensitizer, conventionally known sulfur sensitizers may be used. Preferable sulfur sensitizers include, besides sulfur compounds contained in gelatin, various sulfur compounds, for example, thiosulfates, thio ureas, rhodanines, polysulfide compounds, etc. can be used. As selenium sensitizers, known selenium sensitizers may be used. For example, those compounds disclosed in U.S. Pat. No. 1,623,499, JP-A 50-71325 and 60-150046 may preferably be used.
In the photographic material used in the invention can comprise a variety of compounds for the purpose of preventing fog during manufacture, storage or photographic processing of the light-sensitive material. Those compounds include compounds which are known as stabilizers or anti-foggants in the art. For example, azoles such as benzthiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptobenzthiadiazoles, aminotriazoles, benztriazoles, nitrobenztriazoles, mercaptotetrazoles, such as 1-phenyl-5-mercaptotetrazole, etc.; mercaptopyrimidines, mercaptotriazines, thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes, tetrazaindenes including 4-hydroxy-substituted 1,3,3a,7-tetrazaindenes, pentazaindenes, etc., benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. can be mentioned.
As binder or a protective colloid of the photographic emulsion used in the present invention, gelatin is advantageously used, however, other hydrophilic colloids may also be used. The hydrophilic colloids include, for example, gelatin derivatives, graft polymers comprised of gelatin and other polymers; proteins such as casein, albumin, etc.; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, etc.; sugar derivatives such as sodium alginate, starch derivatives, etc.; synthetic hydrophilic polymers such as polyvinyl alcohol and partial acetal thereof, poly-N-pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole, etc. These polymers may be either homopolymers or copolymers. As gelatin, there may be usable an acid process gelatin as well as lime-processed gelatin. Further, hydrolytic products or enzyme decomposition products of gelatin may also be used. Polysaccharides such as dextrans and dextrins described in JP-A 9-304855 may also be used to enhance rapid processablity.
In the photographic emulsion used in the present invention, for the purpose of improving dimensional stability, etc., synthetic polymers which are water-insoluble, or sparingly water-soluble can be incorporated. For example, alkyl(metha)acrylates, alkoxy(metha)acrylates, glycidyl(metha)acrylates, (metha)acrylamides, vinyl esters such as vinyl acetate, acrylonitrile, styrene, etc. may be used either singly or in combination. Further, these polymers may be used in the form of a copolymer together with other monomer constituents such as acrylic acid, methacrylic acid, xcex1,xcex2-unsaturated dicarboxylic acid, hydroxylalkyl(metha)acrylate, sulfoalkyl(metha)acrylate, styrene sulfonic acid, etc.
The swelling percentage of the light sensitive silver halide emulsion layer side is referred to as an increase in swelling layer thickness of the emulsion layer coating side of a photographic material after the photographic material is immersed into water at 25xc2x0 C. and allowed to stand for 3 min. Thus, the swelling percentage is defined as follows:
[(swelling thickness-coating thickness)/(coating thickness)]xc3x97100 (%)
In the processing method of silver halide photographic materials of this invention, the swelling percentage of the emulsion layer side is preferably 10 to 100%, more preferably 20 to 70%, and still more preferably 20 to 50%.
There are employed various hardeners to adjust swelling of the photographic material used in this invention. Thus, an inorganic or organic hardeners are incorporated as a cross-linking agent for hydrophilic colloidal material such as gelatin into an emulsion or a light-insensitive hydrophilic colloid layer to adjust the swelling percentage of the emulsion layer side. Examples of preferred hardeners include chromium salts (chrome alum, chrome acetate etc.), aldehydes (formaldehyde, glutar aldehyde, glyoxal etc.), N-methylol compounds (dimethylol urea, dimethylol dimethylhydantoin etc.), dioxane derives (2,3-dihydroxydioxane), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis)vinylsulfonyl)methyl ether, N,N-methylenebis-[xcex2-(vinylsulfonyl)propioneamide], etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogenic acids (mucochloric acid, phenoxymucochloric acid, etc.)isooxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinyl gelatin, and carbonyl group-activating type hardeners, singly or in combination thereof. These hardeners are described in Research Disclosure Vol. 176, item 17643 (Dec., 1978), page 26, section A-C.
Various additives are further employed in the photographic material relating to the invention, including a desensitizer, plasticizer, lubricant, development accelerating agent and oil.
A support used in the present invention may be a transparent or nontransparent one, and a transparent plastic resin support is preferred for the purpose of the invention. As the plastic resin support may be employed a support comprising a polyethylene compound (e.g., polyethylene terephthalate, polyethylene naphthalate), a triacetate compound (e.g., triacetate cellulose), or polystyrene compound.
The thickness of the support is preferably 50 to 250 xcexcm and more preferably 70 to 200 xcexcm. To make improvements in roll set curl, it is preferred to subject to heat treatment after casting of base. The treatment is most preferably after casting of base and before emulsion coating, but it may be made after emulsion coating. The condition for the heat treatment at a temperature of not lower than 45xc2x0 C. and not higher than a glass transition temperature and over a period of one second to ten days is preferred. From the point of productivity is preferred a period within one hour.
In this invention, the following compounds are preferably contained in a silver halide photographic light sensitive material.
(1) Dye in the form of a fine solid particle dispersion:
Compounds described in JP-A 7-5629 page 3, [0017] to page 16 [0042].
(2) Compound having an acidic group:
Compounds described in JP-A 62-237445 page 3, left lower column line 11 to page 25, right lower column line 3.
(3) Acidic polymer:
Compounds described in JP-A 6-186659 page 10, [0036] to page 17 [0062].
(4) Supersensitizer:
Compounds described in JP-A 6-347938 page 3, [0011] to page 16 [0066].
(5) Nucleation promoting agent:
Compounds described in JP-A 7-114126 page 32 [0158] to page 36 [0169].
(6) Tetrazolium compound:
Compounds described in JP-A 6-208188 page 8 [0059] to page 10 [0067].
(7) Pyridinium compound:
Compounds described in JP-A 7-110556 page 5 [0028] to page 29 [0068].
(8) Redox compound:
Compounds described in JP-A 4-245243 page 7 to page 22.
(9) SPS support:
Supports described in JP-A 3-54551.
The above described additives and other known additives are referred to Research Disclosure No. 17643 (December, 1978) pages 23 to 29; ibid No. 18716 (November, 1979) pages 648 to 651; ibid No. 308119 (December, 1989) pages 996 to 1009.
Photographic materials used in the invention are processed preferably with an automatic processor having at least four processes of developing, fixing, washing (or stabilizing) and drying.
One feature of this invention concerns the use of the compound of formula (A) earlier described, as a developing agent.
To the developing solution may optionally be added various additives including, for example, an alkali agents such as sodium hydroxide, potassium hydroxide, etc,; pH buffers such as carbonates, phosphates, borates, boric acid acetic acid, citric acid, alkanolamine, etc. A preferred pH buffer is a carbonate in an amount of 0.4 to 1.0 mol/l (and more preferably 0.4 to 0.8 mol/l).
In cases where the compound of formula (A) is used as a developing agent, sulfites are preferably used as a preservative in an amount of 0.02 to 0.9 mol/l (and more preferably 0.1 to 0.3 mol/l).
There are optionally employed solubilizing aids such as polyethylene glycols, esters thereof, alkanolamine, etc.; sensitizers such as nonionic surface active agents containing a polyoxyethylene, quarternary ammonium compounds, etc.; surface active agents, antifoaming agents, anti-foggants such as halide compounds such as potassium bromide, sodium bromide,etc.;nitrobenzindazole, nitrobenzimidazole, benztriazole, benzthiazole, tetrazole compounds, thiazole compounds, etc.; chelating agents such as ethylenediaminetetraacetic acid or alkali salts thereof, nitrilotriacetic acid, polyphosphonic acids, etc.; development accelerators such as those compounds disclosed in the U.S. Pat. No.2,304,025, JP-B 47-45541(hereinafter, the term, JP-B means published Japanese Patent); hardening agents such as glutaraldehyde or metasulfite additives thereof, etc.; anti-foaming agents, etc. The pH of the developing solution is preferably adjusted not less than 7.5 and less than 10.5. More preferably the pH is adjusted not less than 8.5 and less than 10.4. The pH of a developer replenishing solution is preferably higher by 0 to 0.5 (more preferably 0.05 to 0.5, and more preferably 0.1 to 0.5) than that of a developer solution at the start of development. The use of a developer solution exhibiting a pH higher by 0 to 0.5 than that the starting developer solution.
As a fixing solution, any one which are popularly known in the art can be used. The fixing solution is an aqueous solution containing a fixing agent and other additives, and the pH of the fixing solution is usually between 3.8 and 5.8. As the fixing agent, for example, thiocyanates such as sodium thiosulfate, potassium thiosulfate, ammonium thiosulfate, sodium thiocyanate, potassium thiocyanate, ammonium thiocyanate and other organic sulfur compounds which are capable of producing a stable silver complex salts and are known in the art as a fixing agent can be used.
A compound which functions as a hardening agent, including, for example, water-soluble aluminum salts such as aluminum chloride, aluminum sulfate, potassium alum, aldehyde compounds (such as glutar aldehyde or its sulfite adduct, etc.) may be added into the fixing solution.
The fixing solution may contain, if necessary, preservatives such as sulfites or metasulfites; pH buffers such as acetic acid, citric acid, etc.; pH adjuster such as sulfuric acid, or chelating agents capable of softening hard water, etc. It is preferable that the concentration of ammonium ion in the fixing solution is 0.1 mol or less per liter of the fixing solution. Particularly preferable concentration of the ammonium ion in the fixing solution is between 0 and 0.5 mol per liter of fixing solution. As the fixing agent, sodium thiosulfate may be used instead of ammonium thiosulfate. They can also be used in combination. It is preferable that concentration of acetate ion is less than 0.33/liter. There may be applicable any compounds capable of releasing an acetate ion in the fixing solution. Acetic acid or a lithium, potassium, sodium or ammonium salt thereof are preferable. Particularly preferable are sodium salt and ammonium salt. The concentration of the acetate ion is preferably 0.22 mol or less, and more preferably, 0.13 mol or less per liter of the fixing solution.
Under this condition generation of acetic acid gas can be highly restrained. Most advantageously, the fixing solution does not substantially contain any acetate ion at all. The fixing agent contains a salt of citric acid, tartaric acid, malic acid, succinic acid or an optical isomer thereof. As the salt of the citric acid, tartaric acid, malic acid or succinic acid, lithium salt, potassium salt, sodium salt, ammonium salt, etc. can be mentioned. Further, lithium hydrogen salt, potassium hydrogen salt, sodium hydrogen salt, or ammonium hydrogen salt of the tartaric acid; ammonium potassium tartarate; or sodium potassium tartarate, etc. may also be used. Among these, are preferable citric acid, isocitric acid, malic acid and succinic acid and the salts thereof; and the most preferable compound id malic acid or salts thereof.
Photographic materials used in the invention is preferably subjected to washing with washing water containing a cleaning agent including an oxidant or fungicide. Examples of oxidants include metal or non-metal oxides, oxygen acids or their salts, peroxides, and organic acids. From the point of view of the discharge to a drain line are preferred oxygen acids such as sulfuric acid, nitrous acid, nitric acid or hypochlorous acid, and peroxides such as hydrogen peroxide or Fenton""s acid. Hydrogen peroxide is specifically preferred. From the point of view of physical distribution, it is preferred to supply the oxidants in the form of a concentrated solution or solid composition. The form of a concentrated solution is specifically preferred and its oxidant content is preferably 0.1 to 10 mol/l, and more preferably 0.5 to 2.0 mol/l. A concentrated solution or solid composition containing an oxidant is mixed with washing water and then supplied. The concentrated solution or solid composition may be mixed immediately before being introduced into a washing bath or may be mixed directly with washing water in a washing bath. With regard to the timing of replenishing the concentrated solution or solid composition containing an oxidant or water may be a constant replenishment per unit time or replenishment in which the processing amount of photographic materials is detected and replenishing is made in accordance with the processing amount. The addition amount of an oxidant to a washing bath is preferably 0.5 to 10 mol, and more preferably 0.5 to 3 mol equivalent with respect to thiosulfate carried-in by the photographic material.
It is a preferred embodiment to allow a preservative or fungicide to be concurrently present with an oxidant. Fungicides usable in the invention may be any one having no adverse effect on photographic performance. Examples of various bactericides and fungicides include thiazolylbenzimidazole type compounds, isothiazolone type compounds, chlorophenol type compounds, bromophenol type compounds, thicyanic acid or isothiocyanic acid type compounds, acid azide type compounds, diazine or tiazine type compounds, thiourea type compounds, alkylguanidine compounds, quaternary ammonium salts, organic tin or organic zinc compounds, cyclohexylphenol compounds, imidazole or benzimidazole type compounds, sulfamide type compounds, active halogen type compounds such as sodium chloroisocyanurate, chelating agents, sulfite compounds, antibiotic substances such as penicillin. Further, there are usable compounds described in L. E. West, xe2x80x9cWater Quality Criteriaxe2x80x9d Phot. Sci. and Eng., vol. 9 No. 6 (1965); bactericides described in JP-A 57-8542, 58-105145, 59126533, 55-111942 and 57-157244; and compounds described in H. Hamaguchi xe2x80x9cChemistry of Bactericide and fungicidexe2x80x9d (published by Sankyo-shuppan, 1982) and xe2x80x9cAntifungal and Antimold Technique Handbookxe2x80x9d edited by Nihon Bokin-bobai Gakkai (published by Gihodo, 1986).
Examples thereof are shown below but are not limited to these:
1. 5-chloro-2-methyl-4-isothiazoline-3-one
2. 2-(4-thiazolyl)-benzimidazole
3. methyl isothianate
4. 3,5-dichloro-4xe2x80x2-fluoro-thiocarbanilide
5. 4-chloro-3,5-dimethylphenol
6. 2,4,6-trichlorophenol
7. sodium dehydroacetate
8. sulfanilamide
9. 3,4,5-tribromosalicylanilide
10. potassium sorbate
11. benzalconium chloride
12. 1-bromo-3-chloro-5,5-dimethylhydantoin
13. monochloroacetoamide
14. monobromoacetoamide
15. monoiodoacetoamide
16. benzimidazole
17. cyclohexylphenol
18. 2-octyl-isothiazoline-3-one
19. ethylenediaminetetraacetic acid
20. nitrilo-N,N,N-trimethinephosphonic acid
21. 1-hydroxyethane-1,1-diphosphonic acid
22. ethylenediamine-N,N,Nxe2x80x2,Nxe2x80x2-tetramethylenephosphonic acid
23. sodium chlorinated isocyanurate
24. 2-methyl-4-isothiazoline-3-one
25. 10, 10xe2x80x2-oxybisphenoxyarsine
26. 1,2-benzisothiazoline-3-one
27. thiosalicylic acid
These compounds are described in U.S. Pat. Nos. 2,767,72, 2,767,173, 2,767,174 and 2,870,015; British Patent No. 848,130; and French Patent No. 1,555,416, with respect to their synthesis and application to other fields. Commercially available products include, for example, PREDENTOL ON, PERMACHEM PD, TOP-SIDE 800, TOP-SIDE EG5, TOP-SIDE 600 (all of which are available from Permachem Asia Co.), FINE-SIDE J-700 (which is available from Tokyo Fine Chemical Co., ltd.) and Prozel GXL (which is available from I.C.I co.).
In cases where the fungicide is supplied to washing water, the content thereof is preferably 0.01 to 50 g/l, and more preferably 0.05 to 20 g/l. In cases where being contained in a cleaning agent, the content is 0.1 to 50 g/l, and more preferably 1 to 20 g/l, with respect to the cleaning agent.
Preferred as a preservative is a compound including a polyalkleneoxide chain, which is represented by the following formula (Po):
formula (Po)
HO (C2H4O)axe2x80x94(C3H6O)bxe2x80x94(C2H4O)cH
where a, b and c each are a positive integer. The compound represented by formula (Po) is a compound in which propylene glycol is added as a hydrophobic group to ethylenoxide. The average molecular weight (also denoted as Av. M.W.) and the molecular weight of polypropylene glycol (also denoted as PPG M.W.) are preferably 2000 to 8500 and 1400 to 2400, respectively; and the ethylene oxide content of the molecule is preferably 40 to 85% by weight. Specifically, it is preferred that in the formula, a+b is ca. 150 and c is ca. 30. Such compound are also commercially available, for example, as xe2x80x9cPluronic Seriesxe2x80x9d nonionic surfactans (produced by ASAHI DENKA Co., Ltd.), as shown below.
The foregoing compound containing a poly(alkylene oxide) chain is preferably incorporated to washing water in an amount of 1 to 1000 ppm, and more preferably 10 to 100 ppm; and in cases when contained as a cleaning agent, the amount is 0.01 to 10%, and 0.1 to 5%, based on an oxidizing agent.
Examples of preservatives usable in the invention further include phosphoric acid, barbituric acid, urea, acetoanilide, oxyquinoline, salicylic acid, quinolinic acid, and their derivatives and salts. Of these, salicylic acid and its derivatives are preferred.
Chelating agents usable in the invention preferably are those which exhibit a chelate stability constant with a calcium ion of 0.8 to 5.0. The chelate stability constant with a calcium ion is the logarithm of a formation constant of one chelating agent molecule with one calcium ion, which is measured under the condition at a temperature of 20xc2x0 C. and an ionic strength of 0.2. Examples thereof include organic acids such as maleic acid, glycolic acid, gluconic acid, glucoheptanoic acid, tartaric acid, citric acid, succinic acid, salicylic acid, ascorbic acid and erythorbic acid; aminopolycarboxylic acids such as glycine, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and nitrilitriacetic acid, and their derivatives and salts. Organic acids are preferably gluconic acid and citric acid, and preferred aminopolycarboxylic acids are ethylenediaminetetraacetic acid and diethylenetriaminopentaacetic acid. These compound are used preferably in an amount of 0.005 to 0.2 mol, and more preferably 0.005 to 0.1 mol per lit of washing water.
In the invention, there can be employed developer or fixer replenishing solution which is prepared from a solid processing (i.e., developer or fixer) composition. The solid processing composition is in the form of powder, a tablet or granule, which are optionally subjected to a moisture-proofing treatment. A processing composition in the form of a paste or slurry is a semi-liquid form and inferior in storage stability. Those which are accompanied with danger in transportation and is subject to limitation are not included in the solid processing composition used in the invention. Herein, the powder refers to an aggregate of microcrystalline particles, the granules refers to granular material obtained by subjecting the powder to a granulating treatment, having a grain size of 50 to 500 xcexcm, and the tablet refers to one obtained by subjecting the powder to granules to compression treatment to make a given form. Of solid processing compositions described above, the composition in a tablet form is preferably used in terms of the accuracy of replenishment and simplicity in handling.
Next, solidification of the processing composition will be described. The processing composition can be solidified in such a manner that the processing composition in the form of a concentrated solution, fine powder or granules is mixed with a water soluble bonding agent and then the mixture is molded, or the water soluble bonding agent is sprayed on the surface of temporarily-molded processing composition to form a covering layer.
A preferred tablet-making process is to form a tablet by compression-molding after granulating powdery processing composition. As compared to a solid composition prepared simply by mixing the processing composition to form a table, there is an advantage that improvements in solubility and storage stability were achieved and as a result, the photographic performance becomes stable.
As for granulation process which is carried out prior to tablet-making process, any conventionally known method such as fluidized-bed granulation process, extrusion granulation process, compression granulation process, crush granulation process, fluid layer granulation process, and spray-dry granulation process can be employed. It is preferred that the average grain size of the granules is 100 to 800 xcexcm and preferably 200 to 750 xcexcm. In particular, 60% or more of the granules is with a deviation of xc2x1100 to 150 xcexcm. When the grain size smaller, it tends to cause localization of mixing elements and therefore, is undesirable. As hydraulic press machine, any conventional compression molding machine, such as a single-engined compression molding machine, rotary-type compression machine, briquetting machine, etc. may be employed to form a tablet. Compression-molded (compression-tableted) solid processing composition may take any form and is preferably in a cylindrical form from the point of productivity, handleability and problems of powder dust in cases when used in user-side. It is further preferred to granulate separately each component, such as an alkali agent, reducing agent and preservative in the above process.
The processing composition in the form of a tablet can be prepared according to methods, as described in JP-A 51-61837, 54-155038, 52-88025, and British Patent 1,213,808. The granular processing composition can also be prepared according to methods. as described in JP-A 2-109042, 2-109043, 3-39735 and 3-39739. The powdery processing composition can be prepared according to methods, as described in JP-A 54-133332, British Patent 725,892 and 729,862 and German Patent 3,733,861.
In cases where the solid processing composition of the invention, its bulk density is preferably 1.0 to 2.5 g/cm3 from the viewpoint of solubility and the point of effects of the invention. When being not less than 1.0 g/cm3, it is advantageous for strength of the solid composition; and when being not more than 2.5 g/cm3, it is advantageous for solubility. In cases where the composition in the form of granules or powder, the bulk density is preferably 0.40 to 0.95 g/cm3.
The solid processing composition is used at least for a developer or fixer but also usable for other photographic processing chemicals such as a rinsing agent. To overcome the hazardous liquid regulations, a developer or fixer is preferred. All of processing chemicals are most preferably solid composition, but at least developer and fixer preferably are solid compositions
A processing chemical having at least a part solidified and a solid processing chemical each applicable to the invention are included in the scope of the invention. It is, however, preferable that the whole component of these processing chemicals are solidified. It is also preferable that the components thereof are each molded into a separate solid processing chemical and then individually packed in the same form. It is further preferable that the components are packed in series in the order of periodically and repeatedly adding them from the packages.
In cases where the developer is solidified, it is preferable to solidify all of an alkali agent, a developing agent and a reducer and when a developer is tableted, the numbers of the tablets may be not more than 3 tablets and, preferably, a single tablet. When the solid processing chemicals are solidified separately into not less than 2 tablets, it is preferable to pack these plural tablets or granules in the same package.
In cases where the fixer is solidified, it is preferable to solidify all of a fixing agent, a preservative and a hardener such as aluminum salts and when a fixer is tableted, the numbers of the tablets may be not more than 3 tablets and, preferably, a single tablet. When the solid processing chemicals are solidified separately into not less than 2 tablets, it is preferable to pack these plural tablets or granules in the same package. It is specifically preferable to solidify the aluminum salt in terms of its handling.
A moisture-proofed package for tablets or pills may be embodied of such a raw material as given below. As for a synthetic resin material, any one of the following materials may be used; namely, polyethylene (including any one prepared in either a high-pressure method or a low-pressure method), polypropylene (either non-stretched or stretched), polyvinyl chloride, polyvinyl acetate, Nylon (either stretched or non-stretched), polyvinylidene chloride, polystyrene, polycarbonate, Vinylon, Evarl, polyethylene terephthalate (PET), other polyesters, rubber hydrochloride, an acrylonitrile-butadiene copolymer and an epoxy-phosphoric acid type resin (a polymer described in JP-A Nos. 63-63037 and 57-32952), or pulp.
The films of the above-given materials are usually made adhered to each other so as to be laminated. However, these materials may also be formed into a coated layer.
It is further preferable to provide a gas-barrier layer thereto. For example, an aluminium foil or an aluminium vacuum-evaporated synthetic resin is sandwiched between the above-mentioned synthetic resin films.
A total oxygen permeability of the above-mentioned laminated layers is, preferably, not higher than 50 ml/m2 24 hr/atm (at 20xc2x0 C. and 65% RH) and, more preferably, not higher than 30 ml/m2 24 hr/atm.
A total thickness of the above-mentioned laminated layers is within the range of, preferably 1 to 2000 xcexcm, more preferably 10 to 1000 xcexcm and, further preferably 50 to 1000 xcexcm.
The above-mentioned synthetic resin films may be comprised of a single (macromolecular) resin layer or not less than 2 laminated (macromolecular) resin layers.
When packing, binding or covering a processing chemical by making use of a water-soluble film or a binder, the water-soluble film or a binder each preferably applicable thereto include, for example, those comprising a basic material of a polyvinyl alcohol type, methyl cellulose type, polyethylene oxide type, starch type, polyvinyl pyrrolidone type, hydroxypropyl cellulose type, pullulan type, dextran type, gum arabic type, polyvinyl acetate type, hydroxyethyl cellulose type, carboxyethyl cellulose type, sodium carboxymethyl hydroxyethyl cellulose type, poly(alkyl) oxazoline type and polyethylene glycol type. Among them, those of a polyvinyl alcohol type and a pullulan type can more preferably be used from the viewpoint of the covering or binding effect.
From the viewpoints of the preservability of a solid processing chemical, the dissolving time of a water-soluble film and the crystal deposition in an automatic processor, the layer thickness of the water-soluble film is to be within the range of, preferably 10 to 120xcexc, more preferably 15 to 80xcexc, and still more preferably 20 to 60xcexc.
The water-soluble films are preferable to be thermoplastic, because a heat-sealing or supersonic fusing treatment can readily be performed and a covering effect can more excellently be displayed.
The tensile strength of a water-soluble film is to be within the range of, preferably 0.5xc3x97106 to 50xc3x97106 kg/m2, more preferably 1xc3x97106 to 25xc3x97106 kg/m2 and, particularly 1.5xc3x97106 to 10xc3x97106 kg/m2. The tensile strength is measured in the method specified in JIS Z-1521.
A photographic processing chemical packed, bound or covered by a water-soluble film or a binder is preferable to be packed in a moisture-resistive packaging material so as to be protected from a high moisture, a moisture in the air such as rain and mist, and an accidental damage produced by bringing the package into contacting with water by scattering water or by wet hand in the course of storing, transporting or handling the package. The moisture-resistive packaging materials include preferably a film having a thickness within the range of 10 to 150xcexc. The material thereof is preferably at least a material selected from the group consisting of a polyolefin film such as those of polyethylene terephthalate, polyethylene and polypropylene, a sheet of craft paper capable of having a moisture-resistive effect displayable with polyethylene, waxed sheet of paper, moisture-resistive cellophane, glassine, polyester, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyamide, polycarbonate, acrylonitrile and a metal foil such as those of aluminium, and a metallo- polymer. They may also be a compounded material of the above-given material.
In an embodiment of the invention, it is also preferable that a moisture-resistive material is made of a decomposable plastic including particularly a biodegradable or photolyzable plastic.
The biodegradable plastics include, for example, (1) those comprising a natural macromolecule, (2) a microbial growing polymer, (3) a synthetic polymer having a good biodegradation property, and (4) a compound of a biodegradable natural macromolecule to a plastic. The photolyzable plastics include, for example, (5) those having a group made present in the principal chain so as to be excited by UV rays and then coupled to a scission. Besides the above-given macromolecules, those having the two functions of a photolyzing and biodegrading properties at the same time may also effectively be used.
The typical and concrete examples thereof may be given as follows:
(1) natural macromolecules, namely,
A polysaccharide, cellulose, polylactic acid, chitin, chitosan, polyamino acid, and the modified thereof;
(2) microbial growing polymers, namely,
xe2x80x9cBiopolxe2x80x9d comprising PHB-PHV (that is a copolymer of 3-hydroxybutylate and 3-hydroxybarrelate), and microbial growing cellulose;
(3) a synthetic polymer having a good biodegradation property, namely,
polyvinyl alcohol, polycaprolactone and the copolymer or mixture thereof;
(4) a compound of a biodegradable natural macromolecule to a plastic, namely,
a natural macromolecule having a good biodegradation property such as starch and cellulose, which is added to a plastic so that a configuration decaying property can be provided to the plastic.
(5) photolyzable plastics, namely,
those introduced thereinto with a carbonyl group for providing a photodecaying property, and those added thereto with a UV absorbent for accelerating a decaying property.
As for such a decomposable plastics as mentioned above, those publicly described in, for example, xe2x80x9cChemistry and Industryxe2x80x9d, Vol. 64, No. 10, pp. 478-484, (1990); xe2x80x9cThe Kino Zairyoxe2x80x9d, July, 1990 Issue, pp. 23-34; may be used. Besides the above, it is also allowed to use the decomposable plastics available on the market, such as Biopol (manufactured by I.C.I.), Eco (manufactured by Union Carbide Corp.), Ecolite (manufactured by Eco Plastics, Inc.), Ecostar (manufactured by St. Lawrence Starch Co.) and Nackle P (manufactured by Japan-Unicar, Inc.).
The above-mentioned moisture-proofed packaging materials are to have a moisture permeability coefficient of not higher than 10 gxc2x7mm/m2xc2x724 hr and, preferably not higher than 5 gxc2x7mm/m2xc2x724 hr.
Next, there is described the replenishing method in which the replenishing rate of a processing solution is determined based on the proportion of an exposed area per unit are of the photographic material to be exposed.
In general, a developer solution and a fixer solution are stored in each replenishing apparatus and then replenished in accordance with the processing amount and run time of an automatic processor. In cases where a replenisher is liquid, solution which has been diluted inside or outside of the replenishing apparatus may be stored and replenished. Alternatively, a concentrated processing solution may be stored and replenished. In cases where the replenisher is solid, a solid processing composition is dissolved in the replenishing apparatus and the resulting replenishing solution is stored therein and replenished.
In the processing method of this invention, a processing solution is replenished at a replenishing rate which is in proportion to an exposed area per unit area of the photographic material. Information of the proportion of an exposed area per unit area of the photographic material is obtained from an exposure output machine such as an image setter or plotter and the obtained information is fed back to a processing solution replenishing apparatus, then, the replenishing rate of a processing solution is adjusted in accordance with the proportion of the exposed area per unit area of the photographic material. Alternatively, the proportion of a developed area per unit area of a processed photographic material is read and information of the developed area proportion is fed back, as a proportion of an exposed area per unit area of the photographic mater, to the replenishing apparatus so that the replenishing rate of the processing solution is adjusted in accordance with the exposed area proportion per unit area of the photographic material.
The replenishing rate of a processing solution may be determined based on the exposed area proportion by any means. In the case of a developer solution in the processing method of this invention, if the exposed area proportion per unit area is the larger, the higher replenishing rate is preferred. In the case of a fixer solution, if the exposed area proportion per unit area is the larger, the lower replenishing rate is preferred. The developer replenishing rate is preferably 30 to 250 ml/m2 and more preferably 30 to 200 ml/m2. The fixer replenishing rate is preferably 40 to 300 ml/m2, and more preferably 30 to 250 ml/m2.
For example, in cases where the exposed area proportion is 5%, the developer replenishing rate is preferably 30 to 200 ml/m2 and the fixer replenishing rate is preferably 120 to 300 ml/m2; in cases where the exposed area proportion is 20%, the developer replenishing rate is preferably 60 to 250 ml/m2 and the fixer replenishing rate is preferably 90 to 300 ml/m2; in cases where the exposed area proportion is 50%, the developer replenishing rate is preferably 100 to 250 ml/m2 and the fixer replenishing rate is preferably 60 to 250 ml/m2; and in cases where the exposed area proportion is 80%, the developer replenishing rate is preferably 150 to 250 ml/m2 and the fixer replenishing rate is preferably 30 to 200 ml/m2.
The developer replenishing rate or the fixer replenishing rate refers to a rate of replenishing a developer or fixer solution which is identical to a developing or fixing bath solution. In cases where a concentrated developer or fixer solution is replenished along with water, the replenishing rate is the sum of the replenished concentrated developer or fixer solution and the replenished water. In cases where a solid developer or fixer composition is dissolved in water and replenished, the replenishing rate is the sum of the volume of the solid developer or fixer composition and the volume of water. In cases where a solid developer or fixer composition and water are replenished separately, the replenishing rate is the sum of the volume of the solid developer or fixer composition and the volume of water. Specifically, when replenished in the form of solid processing composition, it is preferred to represent the volume of a solid processing composition to be directly fed to the processing bath and the separately replenished water. The developer replenishing solution and the fixer replenishing solution may be the same as the developing tank solution and the fixing tank solution in the processor, or solutions obtained from different solutions or a solid processing composition.
The developing, fixing, or washing and/or stabilizing temperature is preferably 10xc2x0 to 45xc2x0 C. and each temperature may be separately adjusted.
In light of demand for shortening the overall processing time, it is preferable that the total processing time (Dry-to-Dry) from the time when the front end of a film is put into the automatic processing machine to the time when it comes out of the drying zone is between 10 to 70 seconds. The total processing time is referred to as the period of time including all processing steps necessary for processing a black-and-white photographic light sensitive material, such as developing, fixing, bleaching, washing, stabilizing and drying, namely, Dry to Dry time. In the case when the overall processing time is less than 10 seconds, satisfactory photographic performance cannot be achieved due to desensitization or contrast-decreasing. The overall processing time is more preferably 30 to 60 seconds. To stably process large amounts such as 100 m2 or more of the photographic material, the washing time is preferably less than 20 seconds.
In the drying zone of the processor, there is employed a system of drying with hot air. A heat conductive member at 60xc2x0 C. or higher (e.g., a heat roller heated at 60 to 130xc2x0 C.) or a radiation body at 150xc2x0 C. or higher (by directly applying electricity to a tungsten, carbon, nichrome, a mixture of zirconium oxide, yttrium oxide or thorium oxide to heat and emit radiation, or by conducting thermal energy from a resistance type heat generator to a radiation emissive substance such as copper, stainless steel, nickel and various types of ceramics to generate heat or infrared rays) can preferably be used to construct the heating zone.
In this invention, there are preferably used automatic processors provided with techniques or mechanism described below:
(1) Deodorization apparatus described in JP-A No. 64-37560, page 544 (2), left upper column to page 545 (3), left upper column;
(2) Effluent treatment method described in JP-A No. 2-646380, page 388 (2), left lower column to page 391 (5), left lower column;
(3) Rinse bath provided between developing and fixing baths, described in JP-A No. 4-313749, page (18) [0054] to page (21) [0065];
(4) Water replenishing method described in JP-A No. 1-281446, page 250 (2), left lower column to right lower column;
(5) Method for controlling hot air of a processor by detecting atmospheric temperature and humidity described in JP-A No. 1-315745, page 496 (2) right lower column to page 501 (7) right lower column, and JP-A 2-108051, page 588 (2) left lower column to page 589 (3) left lower column;
(6) Method of silver recovery from fixer effluent solution described in JP-A6-27623, page (4) [0012] to page (7) [0071].